SUPPLY AND DEMAND OF LIGHT NAPHTHA AS POTENTIAL PETROCHEMICAL FEEDSTOCK IN SAUDI ARABIA

ABSTRACT

Saudi Arabia is a major crude oil producer and exporter. Additionally, with the completion of its master gas gathering and treatment system petrochemical industries became the Kingdom's second major industrial sector. Currently, the Saudi petrochemical industry depends mainly on (C₁) methane and (C₂) ethane components of associated gas (AG) and natural gas (NG) as feedstocks. A variety of basic petrochemicals are now being produced principally by plants of the Saudi Basic Industries Corporation (SABIC).

There is a necessity of enhancing the use of various under-utilized hydrocarbon resources. At present, one of the favored under-utilized resources and potential candidates for upgrading is light naphtha (LN). Because LN has the advantage of producing a more diverse petrochemical product portfolio than C₁ and C₂ components, it is expected that LN will assume an increasing importance as feedstock in the future development of petrochemical industries in Saudi Arabia. However, industrial opportunities for economies of large-scale production of petrochemicals based on LN might not be favored.

Saudi Arabia's chemical and petrochemical industrial sector has not yet been fully developed, and its production lines are not enough diversified to benefit from LN. The development and expansion of Saudi petrochemical industries usually follows the international trend in this sector, and benefits from its technological achievements. Worldwide global shift in the use of feedstock in this industrial sector will be reflected in the Saudi petrochemical industries. As the world trend is to maximize the utilization of under-utilized petroleum resources, one would expect optimization of LN utilization in Saudi Arabia in the near future.     

RAPID PYROLYSIS OF EASTERN CANADIAN COALS BY FREE FALL REACTORS

The effect of temperature was investigated on the rapid pyrolysis of Prince, Lingan and No. 26 coals in the temperature range of 525^° to 750^°C using a 600 cm high stainless-steel free fall reactor at atmospheric pressure.

The yields of char, condensibles and gaseous products were determined at 25^°C intervals. Gaseous products were analysed for H₂, CO, CO₂, CH₄ and C₂+.

Volatile product (condensible and gas) yields exceeded the volatile product in the A.S.T.M. methods at and above 700^°C.

Some experiments using Prince coal were repeated at reduced pressure (50 mm mercury) in both the 600 cm height stainless-steel and a 140 cm height quartz reactor in order to find out the effect of pressure and retention time.

The experimental results indicated that the condensable yield was higher at the lower pressure and at the shorter retention time. The effect of retention time was far more pronounced.     

ALUMINA SUPPORTED Co-Mo OXIDES AS A CATALYST FOR HYDRODESULPHYRISATION OF ORGANIC SULFIDES AND DISULPHIDES (PART-I) USING STOPPED FLOW GAS CHROMATOGRAPHY

A model study on the hydrodesulphurization of dimethyl sulphide, di n-prophyl sulphide, di n-butyl sulphide and dimethyl disulphide on Co-Mo-A1₂O₃ surface was conducted using stopped-flow chromatographic technique. The plots for the rates of hydrocarbon formation agreed well with the first order reaction at the surface of the catalyst.

Activation energies for the hydrodesulphurization of (C₂H₅)₂S, (C₃H₇)₂S, n-(C₄H₉)₂S and (CH₃)₂S₂ are 57.55, 70.67, 72.74 and 37.80 Kj mole^-1 respectively.     

拓宽SINOALKY硫酸法烷基化技术原料适用范围的工业实践

中国石化洛阳分公司在SINOALKY硫酸法烷基化装置中创造性地在醚后碳四原料中少量掺炼醚前碳四、气分碳五和重整无硫液化气进行工业实践,累积了掺炼各种物料期间装置操作参数变化以及对装置酸耗影响的经验。结果表明：在装置掺炼上述各种物料期间,产品质量全部合格,烷基化油的研究法辛烷值为96.1～96.8,终馏点小于194.2 ℃,蒸气压为42.8～49.5 kPa;掺炼醚前碳四时,烷基化油收率提高7.40百分点;掺炼气分碳五时,烷基化油收率提高2.46百分点。该工业实践拓宽了SINOALKY硫酸法烷基化技术的原料适用范围,为工艺包的改进和炼油厂SINOALKY硫酸法烷基化装置的生产优化提供了新思路。     

ORGANIC MATTER IN PETROLEUM SLUDGES: A SOURCE OF USEFUL MATERIALS Part 1: Separation of Organics and Fractionation by Alkane Solvents

The environmental impact of organics in crude oil sludge discharges and their potential loss as valuable resources, necessitates investigations on their recovery and use.

Organics in sludges deposited from two high API, low sulfur and low asphaltenes, parafinic Libyan crude oils:

(Sedra CO., API = 37, S = 0.39%, Asphaltenes = 0.73%; and :

Hamada CO., API = 39, S = 0.08%, Asphaltenes = 0.28%)

were extracted with toluene using a modified Soxhlet system (MSS).

In addition to organics extraction, toluene azeotroped water impurity, which was then separated in a specially designed side-arm graduated tube receiver in the MSS. Toluene was removed from TSO under low pressure distillation which effected loss of light ends. TSO, 89.3 ±1.6% (Hamada) and 95.4 ±1.2% (Sedra) were determined by evaporation of toluene in a rotavapor under 20 mm Hg ; and after readjusting for lightends loss.

TSO was sub-fractionated with normal pentane (n-C₅) and normal heptane (n-C₇) to insolubles and maltenes fractions. The n-C₅ insolubles were 25.6 ±2.5% and 27.8 ±5.0% and the n-C₇ insolubles were 24.2 ±3.9% and 22.0 ±1.1% in TSO from Hamada and Sedra sludges respectively. Toluene insoluble matter (TIM) and azeotroped water content (AzW) were also determined. Thus the values of TIM: 8.6 ±1.8%, 2.9±1.1%; and AzW : 1.8 ±0.3%, 1.9±0.4for Hamada and Sedra sludges respectively were obtained. Ultimate analysis and ash contents of TSO's, n-C₅ and n-C₇ insolubles and maltenes were also conducted.The big increase in the n-C₅ and n-C₇ insolubles in the TSO from the two, low asphaltenes crude oils is discussed and a mechanism of deposits formation is proposed.     

MOLECULAR SIEVE CARBON FROM COALS FOR AIR SEPARATION

Molecular Sieve Carbon (MSC) for air separation has been prepared from two Chineae coals ( anthracite and bituminous coal) by carbonization followed by activation and carbon deposition. The optimum experimental conditions have been obtained for each coal and the such made MSC could separate N₂ from air efficiently. Also investigated is the preparation of MSC by mixed coals of anthracite and bituminouscoal.

The adsorption of CO₂ and C₂H₆ on the MSC at 298K has been studied. Dubinin theory is used to interpret the isotherms. The predominating micropores of the MSC are those having the size of 0.33-0.40 nm in diameter.     

THERMAL DECOMPOSITION OF SAUDI CRUDE OIL ASPHALTENES

Asphaltenes precipitated by the use of pentane, heptane and decane solvents from Saudi Arabian Light (AL) and Saudi Arabian Heavy (AH) crude oils 370^°C + residua have been investigated by thermal gravimetric analysis and pyrolysis - gas chromatographic analysis at 350^°C and 520^°C. Gas chromatographic analysis of the gases evolved during pyrolysis has shown that CO, CO₂ and CH₄ constitute the major portion of the gases evolved at 350^°C from pentane and heptane asphaltenes of AH residue and from pentane asphaltenes of AL residue. Whereas gases evolved from decane asphaltenes are dominated by CO₂ and C₂-C₄ hydrocarbon gases. At 520^°C, hydrogen and methane represent 56-80 vol %of the gases evolved from all the four asphaltenes. The amounts of C₁-C₄ hydrocarbon gases increased with an increase in the carbon number of the precipitating solvent at 350^°C and decreased at 520^°C. The presence of up to C₃₆ normal alkane hydrocarbon has been indicated in the maltenes produced from these asphaltenes. The loss of nitrogen from AH asphaltenes during pyrolysis remained low (1-6 wt %), whereas the losses of oxygen and sulphur ranged from 58 to 74 wt % and 10 to 29 wt %, respectively.     

REACTION OF PHOSPHORIC ACID WITH THERMAL RESIDUES AND BITUMENS

The purpose of the work was to study the effect of the addition of small quantities of phosphoric acid (or P₂O₅), on the physical and chemical behaviour of petroleum residues and bitumens.

Phosphoric acid (and P₂O₅) reacts only with thermal products such as visbreaker (VB) residues and bitumens, and do not react with straight run (SR) products.

The unstable constituents of VB residues, i.e. carbonaceous material and part of the asphaltenes, contain significant amounts of free radicals which easily share electrons with phosphorous.

The resulting condensed particles are higher molecular wighht, polar material no longher soluble in the bitumen, and flocculate.

This reaction confirms the presence of stable free radicals in thermal bitumens and residues, suggests a way to neutralize their destabilizing effect.     

催化裂化烟气脱硫脱硝装置废水COD超标原因分析及应对措施

针对中国石化海南炼油化工有限公司重油催化裂化烟气脱硫脱硝装置外排废水COD(化学需氧量)超标的问题,通过分析补充新鲜水COD、综合塔补水量、余热锅炉出口烟气中SO2浓度、燃料气中C5+组分浓度、余热锅炉操作条件、废水氧化时间等因素,并采用重整轻汽油加入浆液中试验考察其对亚硫酸盐和亚硫酸氢盐氧化反应的影响.通过综合判断,...     

济阳坳陷深层裂解气成因鉴别及其成藏差异性

济阳坳陷深层裂解气藏成因较为复杂,影响了深层天然气的认识和勘探。利用天然气组分和碳同位素等鉴别了原油裂解气和干酪根裂解气,进一步分析了2类成因的成藏差异性。原油裂解气表现为Ln(C₂/C₃)值随Ln(C₁/C₂)值增大而增大;干酪根裂解气随Ln(C₁/C₂)值的增大,Ln(C₂/C₃)值基本不变。在有机质类型和热演化程度大致相当的情况下,原油裂解气δ¹³C₁值、δ¹³C₂值、δ¹³C₃值与相应的干酪根裂解气的最大差值分别为-12.4‰、-8.8‰和7.5‰;随着δ¹³C₁值或(δ¹³C₁-δ¹³C₂)值的增大,干酪根裂解气(δ¹³C₂-δ¹³C₃)值快速减小,而裂解气(δ¹³C₂-δ¹³C₃)值变化微弱。干酪根裂解气藏表现为早期油气扩散、断裂活动停止和后期天然气充注,原油裂解气藏体现为早期油气充注、岩性侧向封堵和后期古油藏裂解的成藏规律。2种裂解气成因开启了深层天然气勘探的新思路,并指出了其勘探方向,对深层勘探具有重要的指导意义。     

带油环凝析气藏注气吞吐采出流体特征

凝析气藏注气吞吐可提高采收率,但凝析气藏注气吞吐实验一般多研究注气量、注气速度及采收率的变化,而缺乏对注气后采出流体组分变化规律的研究.在建立带油环凝析气藏多次注气吞吐室内物理模拟评价方法的基础上,开展了带油环凝析气藏衰竭式开采后注气吞吐开采实验.结果表明:凝析气注气吞吐开采过程中,随注气吞吐次数增多,产出流体N2+C...     

页岩中丙烷的降解特征及对页岩气组成的影响

为探讨高过成熟阶段页岩中小分子烃类的降解对页岩气组成的影响,选取了丙烷和页岩(取自四川盆地龙马溪组同一钻井、不同深度)开展不同系列的模拟实验。对C_3H_8、C_3H_8+页岩、C_3H_8+页岩+水在360℃、50 MPa条件下进行黄金管限定体系恒温热模拟实验,恒温时间包括72,216,360,720 h;同时为探讨更高演化程度条件下页岩中小分子烃类的降解特征,对C_3H_8、C_3H_8+页岩分别在400,450,500,550℃和50 MPa条件下恒温热模拟72 h。结果显示,360℃恒温实验条件下,C_3H_8+页岩体系中CH_4、C_2H_6生成量及CH_4/C_2H_6值比相应的C_3H_8对照实验高,且黏土矿物含量高的S1系列实验生成的CH_4、C_2H_6及CH_4/C_2H_6值基本较S2系列高。提高模拟实验温度后,丙烷的转化率显著提高,C_3H_8+页岩实验中的CH_4、C_2H_6产率均高于对照实验,且CH_4的产率高于C_2H_6。2个系列的模拟实验结果均说明黏土矿物能催化C_3H_8的裂解,且有利于CH_4的产生。含水体系中CH_4、C_2H_6生成量及CH_4/C_2H_6值比无水体系高,说明水能促进页岩中C_3H_8的裂解,且有利于CH_4的富集。页岩中黏土矿物和水对C_3H_8裂解的促进作用导致页岩气向干燥系数高的方向演化,页岩中小分子烃类的降解对高过成熟阶段页岩气的组成具有重要影响,在此过程中水分子起到重要作用,其对高过成熟页岩气资源的评价值得更多关注。     

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轻烃芳构化是采用油气加工后生成的液态烃（Ｃ３～Ｃ９），在Ｚｎ改质的ＺＳＭ－５沸石分子筛催化剂的作用下（５００℃，常压）发生脱氢、芳构化反应，生成苯（Ｂ）、甲苯（Ｔ）、二甲苯（Ｘ）等混合芳烃，实现低碳烷烃改质的过程。这些混合芳烃既可作高辛烷值汽油的调合剂又可作为化工原料，反应后的副产物还可以综合利用，因此可以显著提高轻烃的应用价值。这种用低碳烷烃制取芳烃的工艺过程不仅为芳烃合成探索了一条新路子，而且也为油田轻烃的高附加值综合加工利用拓宽了途径。为此测试了催化剂的基本物理性质，在１００ｍｌ试验装置上评价了轻烃（Ｃ３～Ｃ９）在Ｚｎ／ＺＳＭ—５上的芳构化，并进行了反应条件的试验，找出了适宜的工艺条件。     

凝析油及其伴生气在运移过程中分异的研究——凝析油运移热模拟生气实验研究

凝析油在地层条件下多呈气相存在,运移过程中除可能有一定的相态转化外,也可能受热力作用进一步裂解成气;温度、介质都对凝析油裂解有促进作用。     

川东北飞仙关组-长兴组天然气几个地球化学问题探讨

基于川东北地区大普光、元坝和通南巴构造带百余个飞仙关组-长兴组天然气样品的分子和碳同位素组成数据,结合烃源岩和储集岩分析资料,就原油裂解气与烃源岩裂解气的区分、烷烃气碳同位素的反序分布和CO₂与H₂S的成因关系等问题进行了探讨。研究结果表明,大普光、元坝区块富含固体沥青的孔洞型气藏的原油裂解气中,丙烷相对较多,以较低的ln（C₂/C₃）值（<3.0）为识别标志。而通南巴等区块裂缝型气藏的烃源岩裂解气（可溶沥青和干酪根的高温裂解气）,具有ln（C₁/C₂）和ln（C₂/C₃）同步升高的组成特征,以较高的ln（C₂/C₃）值（>3.0）与典型的古油藏原油裂解气相区别。各构造带的飞仙关组-长兴组烷烃气存在碳同位素反序分布,可能有多种原因。其中,通南巴构造带河坝场气田飞仙关组烷烃气中的该现象,是由于龙潭组过成熟干气混入志留系气源气所致。飞仙关组-长兴组发生过TSR（硫酸盐热化学还原反应）作用的天然气中,多呈高CO₂、低H₂S和低CO₂、高H₂S两种分布模式,两种非烃气的相对含量受气藏流体-岩石相互作用体系的控制。在高含H₂S的气藏中,CO₂主要来源于烃类的氧化,并经流体-岩石交换作用,其δ¹³C值相对较负;而在CO₂异常丰富的天然气中,CO₂主要由碳酸盐岩的化学分解而来,δ¹³C较重。     

四川盆地天然气的碳同位素特征

四川盆地发育10多个产气层系、6套主要气源岩。文中研究了不同地区不同产层的碳同位素组成特征。大多数气样的δ13C具有正碳同位素系列(δ13C₁<δ13C₂<δ13C₃<δ13C₄),显示出有机成因特征。一些样品中甲乙烷碳同位素倒转(δ13C₁>δ13C₂)可能是由于不同源岩或不同成熟度的气混合的结果。盆地中相同成熟度油型气的δ13C比煤成气的轻。CO₂的δ13C也具有生物成因的特征。      

正丁烷异构反应收率降低原因分析及对策

针对某炼化企业异构反应系统异丁烷收率下降问题进行分析,发现异构化进料以及循环丁烷中C5及C5+重组分质量分数高于3％、四氯乙烯助剂水质量分数高达45μg/g、反应器运行负荷高达115％～120％等是其影响因素;通过控制原料重组分含量及降低循环丁烷中C5及C5+组分质量分数低于2.5％,应用高品质四氯乙烯(水质量分数低于...     

Utilization of sour associated gas

The problem of utilizing sour associated gas and natural gas from small fields is examined. Creation of production of commercial chemical products directly in the field, in particular, reagents against sulfate-reducing bacteria using hydrogen sulfide as feedstock, is proposed as one direction for solving this problem. The results of testing “Advance” biocide, whose production technology is based on the reaction of hydrogen sulfide contained in hydrocarbon gas with another feedstock petrochemical component, are reported. According to the results of a wide series of industrial tests, this biocide is suitable for use in the oil and gas sector.     

HYDRODESULFURIZATION OF QAIYARAH 80-205°C NAPHTHA FRACTION OF ALUMINA SUPPORTED Co-Mo-OXIDES ( PART 2) USING STOPPED FLOW GAS CHROMATOGRAPHY

Effective desulfurization of Qaiyarah 80-205°C, naphtha fraction resulted on alumina supported Co-Mo oxides, assembled in a GC column using H₂ as a carrier gas and the stopped-flow technique. Over 90% of 3ulfur vas removed from this partially cracked naphtha and a similar result (Ca 90%) was obtained when hydrodesulfurizing an acid-base treated naphtha.

1_H nmr studies on the chromatographically separated hydrodesulfurized fractions revealed interesting structural parameters leading to suggestions related to the occurrence of a reforming reaction and the liberation of fresh H₂ gases which further promotes hydrodesulfurization.     

准噶尔盆地东南部石炭系规模烃源岩的发现及天然气勘探潜力

准噶尔盆地天然气资源丰富,但探明程度低.盆地东南部阜26井石炭系 自生自储气藏的发现揭示了一个崭新的天然气勘探领域.准噶尔盆地东南部上石炭统巴塔玛依内山组发育一套煤系烃源岩,其岩性主要为碳质泥岩和煤系泥岩,含少量煤.碳质泥岩和煤的氢指数平均为182mg/g,部分样品的有机显微组分中壳质组和腐泥组含量之和达20％以上,有...