SHORI COAL LIQUEFACTION AND ITS CO-PROCESSING WITH PETROLEUM RESIDUE

Shori coal from China shows an excellent applicability to liquefaction. The reactivity to liquefaction of Shori coal is proved to show higher temperature-dependence than those of Wandoan coal and Battle River coal. Anthracene oil has an excellent solvent effect as a vehicle oil. However, Shori petroleum residue shows a comparable effect as a vehicle oil to anthracene oil at 450°c. Hydrogen contents in the hexane-soluble fraction produced from co-processing with Shori petroleum residue are higher than the hydrogen contents in the hexane-soluble fraction produced when anthracene oil was used. Shori petroleum residue seems to be associated with the lowering of the nitrogen content and oxygen content in the hexane-soluble fraction. But the sulfur in Shori petroleum residue was transferred to the hexane-soluble fraction.     

COAL LIQUEFACTION WITH ANTHRACENE OIL. INFLUENCE OF SOLVENT PRETREATMENT,TEMPERATURE, CATALYST AND PRESSURE

ABSTRACT

The effect of solvent pretreatment, temperature, a CoMo/Al₂O₃ catalyst and pressure on coal liquefaction with anthracene oil has been evaluated. The experiments were conducted in a 500 ml autoclave with 10 g of a Spanish subbituminous A coal. 30 g of solvent, 1 hour reaction time and 400 rpm stirring speed. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes using pentane, toluene and THF as extractive solvents. The behaviour of anthracene oil as coal liquefaction solvent is very much enhanced by prehydrogenating it and by the addition ot an active catalyst. The influence of temperature depends on the operating conditions such as solvent pretreatment, catalyst, pressure etc. The addition of an active catalyst greatly improves conversion and the quality of the liquefaction products and diminishes repotimerization reactions. Hydrogen pressure is essential for coal liquefaction with anthracene oil, although over 16 MPa no further increase in coal conversion is observed.     

EXTRACTION ENHANCEMENT OF COAL THROUGH CHEMICAL REACTIONS WITH CETENE AND CETANOL IN THE ANTHRACENE OIL UNDER ATMOSPHERIC PRESSURE CONDITIONS

ABSTRACT

Assam coal has been reacted with cetene or cetanol in anthracene oil. These reactions were attempted to alkylate the coal in the absence of a catalyst under the conditions of extractive disintegration of coal. Coal derived chemicals were used in the reactions as far as possible. The reactions resulted in enhancing the extractability of coal in quinoline by more than 70–90%. These reactions resulted in the alkylation of coal and increase of carbon contents in coal along with the addition of nitrogenous bases from anthracene oil to coal.     

RHEOLOGICAL PROPERTIES OF COAL OIL MIXTURES: INFLUENCE OF COAL PROPERTIES

ABSTRACT

The effect of coal properties on the rheological properties of coal oil mixtures (COM) has been studied. Coal samples having different ash and moisture contents have been used to study the effect of these components on rheological properties of coal oil mixtures. It has been observed that coals having higher ash content give rise to less viscous coal oil mixtures and viscosity of the COM decreases as moisture content of coal is reduced.     

LIQUEFACTION AND THE CHARACTERIZATION OF COAL DERIVED LIQUIDS OF MENGEN LIGNITE

ABSTRACT

The liquefaction characteristics of Mengen lignite has been investigated in the presence of cobalt-molybdenum on alumina catalyst in a 1 lt batch autoclave system with anthracene oil used as solvent. The experiments were carried out in the range of 15–60 atm for initial hydrogen pressure, 360–440°C for reaction temperature, 1–5 for solvent to coal ratio and 0–20% of coal for catalyst loading which were chosen as process variables. Coal particle size and reaction time were kept constant as below 200 mesh and 30 minutes respectively, (Erdem 1987)

The product was analyzed in terms of total conversion, liquid yield and liquid product distribution determined as preasphaltenes, asphaltenes and oils. The oil fraction was further separated by column chromatography while the asphaltenes were separated into basic and acid/neutral fractions. The preasphaltenes were divided into two fractions as carbene (CS₂ solubles) and carboid (CS₂ insolubles). (Inanç 1989)

The oil yield is mostly affected by the catalyst loading which shows to a certain extent that the conversion of asphaltenes to oils is a catalytic step. The selected process variables showed a positive trend with respect to the yield of hexane eluted oil which is the desired product of liquefaction.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 4. COAL CO-PROCESSING USING SUGAR CANE BAGASSE OIL AS SOLVENT

Abstract

In the present work, coal co-processing with sugar cane bagasse oil was studied for the first time. Sugar cane bagasse was chosen due to its great offer, since it is a residue in the process of a large project named PROALCOOL aiming the producing ethanolfrom sugarcane. In addition, the liquefaction of sugar cane bagasse with monoethanolamine was already developed in our laboratory showing good results. Four coal samples were studied. The yields of the total conversion and the oil productions were obtained in order to evaluate the efficiency of the liquefaction process studied.     

STRUCTURAL GROUP ANALYSIS OF PRODUCTS FROM TWO-STAGE LIQUEFACTION OF HIGHVALE COAL

ABSTRACT

Products from liquefaction of Highvale Coal (Alberta. subbituminous) in anthracene oil and recycled product, with iron oxide catalyst, were studied using a structural group analysis method. The various functional groups were determined using a combination of proton NMR. carbon-13 NMR. IR. elemental analysis and nitrogen titration analysis. The liquefaction reactions in anthracene oil and in recycled product oil were compared on the basis of three solvent quality Indices and the predominant structural groups in the resulting liquids. The results show that major structural changes occur at both stages of liquefaction. Processing in anthracene oil showed much greater structural changes than liquefaction in the recycled product. The structural profiles Indicated a reduction in aromatic structures and a dramatic increase in aliphatic and naphthenic structures during processing in anthracene oil. These changes were attributed to the hydrogenation of aromatic structures and the dissolution of aliphatic and naphthenic compounds. Liquefaction in recycled product showed less significant changes in structural composition but resulted in a better quality product in terms of the amount of distillable oils, transferable protons and hydrogen to carbon ratio. This improvement was attributed to the improved availability of donatable hydrogen in the recycled product.     

TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

ABSTRACT

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

Methods of analysis modified size exchange chromatography method for analysis of heavy oil residues

A modified size exchange chromatography method is used to obtain molecular weight distributions, average molecular weight, and other characteristics of heavy oil residues: coal asphalt, petroleum asphalt, vacuum residue oil, and ethylene residue oil. This method can be applied for developing and studying processes involved in hydrogenation of heavy oil residues, road asphalt production, and coal liquefaction.     

Removal of Naphthenic Acids of a Second Vacuum Fraction by Catalytic Esterification

Abstract

This article introduces a catalytic esterification process to reduce the acid number of a high acid content petroleum fraction. The fraction was treated with methanol under conditions sufficient to form the naphthenic acid esters. In this way, the acid number of the petroleum fraction could be lowered. SnO could accelerate petroleum oil esterification. The acid removal ratio was much higher in the presence of SnO than without it. The optimal reaction conditions were: reaction temperature 300°C, the quantity of methanol in oil was 5.0 wt%, the quantity of catalyst SnO was 4.0 wt%, and a longer reaction time was preferable.     

PYROLYSIS AND LIQUEFACTION OF BRAZILIAN COAL AND COAL-DERIVED ASPHALTENES

ABSTRACT

The present work describes a study of the liquefaction and pyrolysis of a Southern Brazilian mineral coal and its derived asphaltenes, using conversion systems developed in our laboratory.

The results show that significant quantities of the intermediate polarity fraction named resins is obtained through the pyrolysis of coal, while after the liquefaction process higher quantities of the higher fractions was found. A model is proposed to explain the liquefaction and pyrolysis processes of both coal and coal-derived asphaltenes.     

LIQUEFACTION OF ELBI˙STAN AND YATAĞAN LIGNITES I N CARBON MONOXIDE/HYDROGEN GAS MIXTURES

Abstract

Thc effects of experimental parameters on the liquefaction yields of Elbistan and Yatagan lignites vcre investigated by using different solvents, guses and catalysts.

In hydroliquefaction of Elbistan lignite with anthracene and creosote oils, higher oil yields were obtained with anthracene oil. Based on this result, anthracene oil was chosen as solvent for further work done with Elbistan lignite. First the effect of moisture in lignite samples vas observed with synthesis gas as medium gas: then, the effect of carbon monoxide/ hydrogen ratio in liquefaction gas mixture was determined using moist lignite samples. The highest oil yield was obtained with moist lignite sample in 3CO/IH₂gas mixture and it was 57.3 % (daf).

The hydroliquefaction oil yields of Yatagan lignite obtained with creosote oil were higher than those obtained in anthracene ail. On Further work done with Yatagan lignite, creosote oil was chosen as solvent. First, the effects of CoMo and red mud catalysts, then in catalyzed medium, the effects of moisture in lignite samples and at last, using moist lignite samples and red mud catalyst. the effects o f carbon monaxide/hydrogen in synthesis gas medium and also, the increase in the oil yield a s an effect of catalyst presence, increased further: the 3CO/lH, ratio in gas medium was suitable for obtaining higher oil yields; and also for obtaining high oil yields, 440°c could be taken a s the most suitable temperature value and the pressure should be increased a s much as technical and economical conditions permit.     

COAL LIQUEFACTION WITH ANTHRACENE OIL. INFLUENCE OF SOLVENT PRETREATMENT, TEMPERATURE, CATALYST AND PRESSURE

The effect of solvent pretreatment, temperature, a CoMo/Al₂O₃ catalyst and pressure on coal liquefaction with anthracene oil has been evaluated. The experiments were conducted in a 500 ml autoclave with 10 g of a Spanish subbituminous A coal. 30 g of solvent, 1 hour reaction time and 400 rpm stirring speed. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes using pentane, toluene and THF as extractive solvents. The behaviour of anthracene oil as coal liquefaction solvent is very much enhanced by prehydrogenating it and by the addition ot an active catalyst. The influence of temperature depends on the operating conditions such as solvent pretreatment, catalyst, pressure etc. The addition of an active catalyst greatly improves conversion and the quality of the liquefaction products and diminishes repotimerization reactions. Hydrogen pressure is essential for coal liquefaction with anthracene oil, although over 16 MPa no further increase in coal conversion is observed.     

沸腾床加氢技术在煤直接液化油加氢改质中的应用

为解决煤直接液化油由于胶质、沥青质含量高且含固体杂质而较难进行加氢稳定处理的问题,采用沸腾床加氢技术对煤直接液化工艺得到的生成油进行加氢稳定处理。工业化应用结果表明：在实际原料明显较设计原料偏重的情况下,目的产品的性质仍然与设计值相符,装置的加氢效果符合设计要求;经过沸腾床加氢工艺处理后,煤直接液化重油的硫、氮含量大幅降低,胶质脱除效果明显,碳率从55.86%降低到38.30%,降低了17.56百分点,装置的芳烃饱和反应深度符合设计要求;催化剂国产化后,性能优于进口催化剂,且保持较高的长周期运转活性。沸腾床加氢技术能够很好地解决煤直接液化油加氢改质的难题,该技术在煤直接液化工艺中应用成功。     

CHARACTERIZATION OF SELENIUM CATALYST FOR COAL LIQUEFACTION IN TERMS OF HYDROGENATION AND CRACKING ABILITY

ABSTRACT

The activities of selenium and zinc chloride catalysts upon transferable hydrogen in coal have been investigated by ^IH-NMR. Se is more active than ZnCl₂ for hydrogen transfer in the coal/anthracene system. The change of radical concentration was monitored by high temperature ESR. It was confirmed that radical concentration in the coal/Se system is greater than that in the coal/ZnCl₂ system at the early stage of pyrolysis. It was concluded that Se has a higher cracking activity as well as hydrogen transfer ability and there is the potential for the use of Se as a catalyst for coal liquefaction.     

LIQUEFACTION OF CELLULOSIC WASTE V. WATER FORMATION AND EVALUATION OF PYROLYTIC CHAR AS A BY —PRODUCT OF PYROLYSIS REACTION

ABSTRACT

Liquid hydrocarbon oil and water have been produced from the liquefaction of cellulosic matter present in municipal solid wastes (MSW). Gases and residual char have also been produced as by-products resulting from the pyrolysis reaction of cellulose. Quantities of water and pyrolytic char were estimated at different conditions of the process (temperature pressure of hydrogen, carrier oil medium and concentration of boric acid). From the results obtained, it was suggested that the formation of water seems to be sensitive to the operational conditions which enhance a water-gas shift reaction (in which water molecules are consumed to produce carbon dioxide and hydrogen). Decreasing of the undesired chary by-product could be achieved by increasing the concentration of boric acid that catalyzes the liquefaction reaction. Two petroleum distillates, namely gas oil and residual fuel oil, were used as carrier media of a solid refuse. It was found that fuel oil is more efficient as a buffering medium that prevents cellulose macromolecules from a rapid and complete charing during the liquefaction process. The pyrolytic char was characterized and evaluated by means of different analytical procedures and solvent extraction using petroleum ether 40–60°C and methanol. Calorific value of the pyrolytic char was found to be 4.6 Kcal g^?1 which is quite close to that of a brown coal. Dropping point test of the extracted material by petroleum ether indicated that the extract can be utilized for producing lubricating greases via saponificattion with a salt of sodium or calcium.     

掺兑蒽油加氢制备煤直接液化循环溶剂

在煤直接液化循环溶剂加氢原料中掺兑煤焦油蒽油,采用300 mL固定床加氢实验装置考察蒽油掺兑量对循环溶剂性质的影响;采用05 L高压釜煤液化实验考察蒽油掺兑量对煤液化反应的影响。结果表明,在相同的加氢条件下,在煤直接液化循环溶剂加氢原料中掺兑5%(质量分数)的蒽油,循环溶剂的芳碳率(fa)降幅337%,供氢指数(PDQI)增幅368%,供氢性能得到提高,但加氢反应氢耗增加,循环溶剂密度、黏度及硫、氮含量增大。采用此循环溶剂进行煤液化时,煤的转化率提高了015%,煤液化油收率增加了098%。随着蒽油掺兑质量分数的增加,循环溶剂供氢性能逐渐减弱,煤液化转化率和液化油收率逐渐减小,循环溶剂密度、黏度及硫、氮含量持续增大。     

DIFFERENTIAL THERMAL ANALYSIS OF COAL IN NON-FLOWING AIR

ABSTRACT

The DTA studies in air are reported on some Indian coals and a lignite. Extraction of coal in quinoline or in liquid paraffin was found to result in the coal residues having higher ignition temperature than that of the original coal. However, extraction of coal in anthracene oil or successive extractive disintegration of coal in anthracene oil, in quinoline and in liquid paraffin was found to yield residual coals having higher reactivities towards oxygen in air as understood from the fact that the ignition temperature of these residues was lower than that of the original coal. DTA studies also supported the degradation of coal as a result of acidic depolymerization reaction.     

GAS CHROMATOGRAPHIC AND IR SPECTRAL STUDIES OF THE PRODUCTS OBTAINED FROM EXTRACTIVE DISINTEGRATION OF COAL

ABSTRACT

Assam coal was extracted in anthracene oil, in quinoline and in liquid paraffin. The gases evolved during the extraction/reaction of Assam coal in anthracene oil and in liquid paraffin, were analyzed using a gas chromatograph. The IR spectra of residual coals were compared with the IR spectrum of original Assam coal. An increase in absorption at 710 cm^?1, decrease in 2940-2860 cm^?1 and increase in nitrogen contents of residual coal was observed in the residual coal obtained from the extractive disintegration.     

煤焦油馏分油用作煤直接液化起始溶剂的加氢稳定研究

 采用煤焦油馏分油中的洗油与脱晶蒽油以质量比1:1混合的油为原料,在处理量500kg/h的加氢稳定中试装置上进行洗油与脱晶蒽油混合油的加氢稳定实验。利用常温常压旋转黏度仪测定混合油加氢所得溶剂的黏度,考察其成浆性能;采用0.5L搅拌式高压釜考察了混合油不同次数加氢所得溶剂的煤直接液化反应效果。结果表明,洗油与脱晶蒽油的混合油经过加氢处理后,表观黏度降低,用来配制油煤浆表现出良好的成浆性能;用作煤直接液化溶剂具有较强的供氢性能,以经过3次加氢后所得溶剂作为煤液化溶剂,可得到89.47%煤液化转化率,63.06%油收率。洗油和脱晶蒽油混合油加氢后所得溶剂是一种效果良好的煤直接液化开工用起始溶剂。