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.     

催化裂化芳烃萃取油用作煤液化起始溶剂

选用一种催化裂化（FCC）芳烃抽提装置生产的芳烃萃取油作为煤液化开车起始溶剂的原料，在0．1t／d连续装置上进行煤液化实验。利用色质联用仪解析其组成和结构，应用常温常压黏度仪考察了其成浆性。结果表明，芳烃萃取油具有多环芳烃含量高的特点，3次加氢后的芳烃萃取油与煤液化加氢循环溶剂的结构组成十分接近，采用3次加氢萃取油制备的煤浆具有良好的成浆性、输送性和反应性，与煤液化加氢循环油参与煤液化的效果相当，是理想的煤液化起始溶剂。     

EFFECT OF IRON CATALYST ON THE COMPOSITION OF OIL FROM COAL LIQUEFACTION

The effect of two iron catalysts, red mud and CGS S-G, as well as C0-Mo/AI₂O3 and Ni-Mo/Al₂03 commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450^°C under initial hydrogen pressure of 85kg/cm² G with tetralin to coal weight ratio of 3. From the results obtained at 450^°C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.     

EFFECT OF IRON CATALYST ON THE COMPOSITION OF OIL FROM COAL LIQUEFACTION

ABSTRACT

The effect of two iron catalysts, red mud and CGS S-G, as well as C0-Mo/AI₂O3 and Ni-Mo/Al₂03 commercial catalysts on the composition of oil derived from the liquefaction of Japanese subbituminous coal have been investigated comparatively by conventional autoclave experiments at 440 and 450^°C under initial hydrogen pressure of 85kg/cm² G with tetralin to coal weight ratio of 3. From the results obtained at 450^°C, total conversion and the yield of gas revealed almost same level with four catalysts, but the oil product from molybdenum catalysts showed higher yield than that from iron catalysts. CGS S-G catalyst also showed higher yield of oil product than red mud catalyst. Reaction behavior of two iron catalysts were also tested by solvent recycle mode experiments.     

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

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.     

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.     

INFLUENCE OF TEMPERATURE AND SOLVENT ON THE PRECIPITATION OF ASPHALTENES

Asphaltenes has been precipitated from a Kuwait flash residue using different n-alkanes (n-C5 to n-C8) at various temperatures ranging from 4^°C to reflux temperatures of the used precipitants. Structures in the asphaltene fractions has been revealed using U.V. fluorescence spectroscopy, elemental analysis and to some extent 1H-nmr. These analysis shows that asphaltenes precipitated in the same amount but at different temperature and with different solvents have merely the same composition. For all n-alkanes the curves of precipitated amount versus temperature show maxima at about 25^°C, implying a shift in the solubility of the asphaltenes.The impact of alkane chain length on the aggregation of asphaltenes through hydrogen bonds is discussed using the alkane-alcohol system as a model. The asphaltene solubility is discussed with the help of the Scatchard-Hildebrand equation.     

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.     

煤炭直接液化起始溶剂油的研究

针对神华集团有限责任公司在建的煤直接液化示范工程所需起始溶剂量大、煤炭焦化产溶剂不足的问题,在0.1 t/d小试装置(BSU)和6.0 t/d工艺开发装置(PDU)上对重油催化裂化回炼油芳烃抽提装置生产的重芳烃作为煤炭直接液化的起始溶剂进行考察.结果表明,重油催化裂化回炼油芳烃抽提装置生产的重芳烃经过多次加氢处理后,其密度和组成与煤液化自产溶剂类似,可以作为煤炭直接液化装置的起始溶剂.在PDU上使用该溶剂,当压力为17 MPa、反应温度为450 ℃左右时,煤转化率达90.42%,液化油收率为56.04%.     

温度压力对水泥浆流变性的影响规律研究

温度与压力是影响水泥浆流变性的客观关键因素。选取了有一定代表性的4种水泥浆,测定了在不同温度、压力下的流变性,根据试验结果,分析了温度、压力对水泥浆流变曲线、水泥浆流型、流变参数及水力参数的影响。研究表明,实际的注水泥流变学设计应考虑温度、压力对水泥浆流变性的影响,温度对流变性的影响要比压力显著得多。     

煤直接液化加氢稳定油加氢生产工业白油研究

以煤直接液化加氢稳定油为原料,采用两种型号的加氢精制催化剂匹配进行两段加氢精制生产工业白油的试验研究。结果表明：在一段加氢精制反应过程中,反应温度、反应压力和体积空速的变化对脱硫、脱氮和芳烃饱和反应有较大的影响,在反应压力为15 MPa、反应温度为380 ℃、体积空速为0.4 h-1的工艺条件下,产品油中的硫、氮质量分数分别为1.6 μg/g和1.5 μg/g,脱硫率和脱氮率分别达到97.72%和99.81%,此时产品中的芳烃质量分数为31.2%,芳烃饱和率为55.9%;二段深度加氢精制后,产品油中的芳烃质量分数可以降低到5%以下;最终的加氢产品油在实沸点蒸馏装置上切割后,得到的280～300 ℃、300～320 ℃馏分油能分别满足5号、7号工业白油（Ⅰ）的行业标准要求。     

煤炭直接液化油品加氢稳定和加氢改质的试验研究

对神华上湾煤直接液化油品进行了加氢稳定和加氢改质的试验研究。煤液化重油经过加氢稳定处理后,可以生产出煤液化需要的供氢溶剂;煤液化轻油经过加氢稳定处理后,中间馏分油的十六烷值低、密度高,还需进一步加工。加氢改质是一种有效改善油品质量的方法。结果表明,加氢改质后小于150 ℃石脑油馏分是很好的催化重整原料,大于150 ℃柴油馏分性质满足环烷基原油生产的轻柴油国家标准;加氢改质柴油馏分对十六烷值改进剂具有良好的感受性,添加1 000 g/g的十六烷值改进剂可以生产出满足欧Ⅱ排放标准的柴油产品。     

溶剂精制对焦化蜡油和催化回炼油催化裂化反应性能的影响

采用糠醛对辽河超稠原油直接延迟焦化得到的劣质焦化蜡油及其与催化回炼油的混合油进行溶剂精制,并在连续反应-再生催化裂化中型实验装置中进行了溶剂精制前后劣质焦化蜡油及其与催化回炼油混合油的催化裂化反应。结果表明,在精制油收率67%～70%的条件下,溶剂精制法可脱除劣质焦化蜡油中78%～85%的氮和36%～39%的芳烃、胶质及沥青质。劣质焦化蜡油及其与催化回炼油的混合油溶剂精制后,其催化裂化反应转化率大幅度提高。精制油的催化裂化反应性能优于辽河渣油催化裂化（RFCC）原料,与RFCC原料掺炼后,轻质油产率提高,生焦率下降,产品质量明显改善。     

煤担载高分散铁镍催化剂在煤/重油加氢共炼中的活性研究

采用沉淀-空气氧化法制备煤担载型高分散铁基催化剂（Fe/C），并引入第二金属镍得到Fe-Ni/C催化剂。采用XRD,HRTEM,SEM-mapping等分析了催化剂的晶相组成、形貌特征及活性金属在煤上的分散状态，高压釜实验对比了两种催化剂在煤/重油加氢共炼反应中的催化活性，分析了反应后固体残渣的微观形貌。结果表明，Fe/C催化剂的主要活性成分为ɑ-FeOOH和γ-FeOOH，引入镍后则生成了混晶相Fe0.67Ni0.33OOH，Fe、Ni活性金属在载体煤表面分布均匀。两种催化剂作用下的干基无灰煤转化率均高于97%，但Fe-Ni/C催化剂作用下产物分散性更好。固体残渣的SEM照片对比表明Fe/C催化剂体系中生成了较多球形焦炭，而Fe-Ni/C催化剂较强的加氢作用能有效抑制共炼体系中裂解中间产物的缩合生焦，在得到较高煤转化率的同时能有效降低固体残渣的粒径。     

RHEOLOGICAL PROPERTIES OF COAL OIL MIXTURES: INFLUENCE OF COAL PROPERTIES

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.     

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.     

制备条件对煤临氢液化催化剂晶相组成的影响

以FeSO₄·7H₂O为铁源,采用沉淀-氧化法在不同条件下制备煤临氢缓和液化的煤载铁系催化剂,利用X射线衍射、扫描电镜和N₂吸附-脱附对催化剂进行表征,探究制备温度、制备时间、铁煤比对催化剂晶相组成、分布和活性的影响。结果表明：随着制备温度升高,催化剂的α-FeOOH和γ-FeOOH晶相结晶度提高,进一步升高温度,催化剂晶相向低活性的γ-Fe₂O₃转化;在适宜制备时间内增加制备时间可以提高催化剂中α-FeOOH和γ-FeOOH晶相的结晶度,制备时间过长时会生成少量γ-Fe₂O₃晶相;较小的铁煤比有利于生成α-FeOOH和γ-FeOOH晶相,但铁煤比过小会使催化剂中α-FeOOH和γ-FeOOH晶相的结晶度降低,铁煤比过大时会生成γ-Fe₂O₃晶相。     

DIRECT LIQUEFACTION OF WOOD BY CATALYST AND WATER

ABSTRACT

Wood powder suspended in water was directly liquefied in the presence of nickel carbonate or potassium carbonate without a reducing agent like hydrogen and/or carbon monoxide. Heavy oils with carbon and hydrogen contents of about 80% were produced and their heats of combustion ranged from 29.3 to 33.4 MJ/kg. Total carbon recovery in the form of heavy oils was about 24%.     

异构脱蜡催化剂及工艺条件对润滑油基础油黏度指数的影响

以中国石油大庆炼化分公司轻质低含蜡油和重质高含蜡油为原料,用开发的PIC系列异构脱蜡催化剂,并配套使用某工业加氢预精制和补充精制催化剂,进行加氢预精制-异构脱蜡-补充精制试验,考察加氢预精制过程及异构脱蜡催化剂和工艺条件对润滑油基础油黏度指数的影响。试验结果和工业装置运行数据表明：通过对异构脱蜡催化剂的改进,催化剂中B酸含量增高;B酸含量、加氢精制温度、异构脱蜡温度的升高,均可提高催化剂的开环活性,进而提高产品黏度指数;与上一代异构脱蜡催化剂PIC-802相比,PIC-812催化剂的活性提高,在工业装置上加工大庆650SN糠醛精制油和200SN浅度脱蜡油时,反应温度分别降低2 ℃和26 ℃,基础油收率均提高4百分点,黏度指数均提高4个单位。