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.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 6. SIMULATED DISTILLATION OF OILS OBTAINED FROM COAL CO-PROCESSING WITH SUGAR CANE BAGASSE OIL

In this paper simulated distillation employing HRGC (high resolution gas chromatography) was used to evaluate the quality of the oils obtained from coal co-processing using sugar cane bagasse oil as the process solvent. Four coal samples were used, two of them corresponding to Brazilian coals, one to an American coal and one to a Polish coal. The results shows that the oil produced through co-processing with sugarcane bagasse oil presents characteristics of lighter oils than those obtained by direct liquefaction of coal with monoethanolamine as solvent.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 6. SIMULATED DISTILLATION OF OILS OBTAINED FROM COAL CO-PROCESSING WITH SUGAR CANE BAGASSE OIL

Abstract

In this paper simulated distillation employing HRGC (high resolution gas chromatography) was used to evaluate the quality of the oils obtained from coal co-processing using sugar cane bagasse oil as the process solvent. Four coal samples were used, two of them corresponding to Brazilian coals, one to an American coal and one to a Polish coal. The results shows that the oil produced through co-processing with sugarcane bagasse oil presents characteristics of lighter oils than those obtained by direct liquefaction of coal with monoethanolamine as solvent.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 5. CHARACTERIZATION OF THE OILS OBTAINED FROM COAL CO-PROCESSING WITH SUGARCANE BAGASSE OIL

In the present work, the chemical characterization of the oils obtained from liquefaction of different coals with sugar cane bagasse oil and also from the liquefaction of coal with monoethanolamine are presented. Characterization of the oil samples was done with the add of spectroscopic and chromatographic techniques, including UV-vis, FTIR, NMR, preparative liquid chromatography (PLC) and high resolution gas chromatography (HRGC).     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 5. CHARACTERIZATION OF THE OILS OBTAINED FROM COAL CO-PROCESSING WITH SUGARCANE BAGASSE OIL

Abstract

In the present work, the chemical characterization of the oils obtained from liquefaction of different coals with sugar cane bagasse oil and also from the liquefaction of coal with monoethanolamine are presented. Characterization of the oil samples was done with the add of spectroscopic and chromatographic techniques, including UV-vis, FTIR, NMR, preparative liquid chromatography (PLC) and high resolution gas chromatography (HRGC).     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 8. DIRECT LIQUEFACTION WITH N-ALCOHOLS

ABSTRACT

The liquefaction of sugar cane bagasse has been an important approach to produce liquid fuels and chemical feedstocks from biomass. In the present work a process has been investigated using a series of n-alcohols such as methanol, ethanol, propanol, butanol and pentanol as the conversion media. The liquefaction studies were made in an autoclave containing the bagasse and the solvent, pressurized with hydrogen (-70 bar) and heated to 370°C for 60 minutes. The products were fractionated by preparative liquid chromatography in order to study the group-type distribution. The results obtained from liquefaction of sugar cane bagasse by ethanol suggests that this could be a good option as an alternative fuel source.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 7. CATALYTIC LIQUEFACTION IN MONOETHANOLAMINE (MEA) AND PRELIMINARY FRACTIONATION OF THE OBTAINED PRODUCTS

The liquefaction of sugar cane bagasse in monoethanolamine (MEA) in the presence of catalysts (zeolite A, non-zeolitic aluminosilicate and zinc chloride) as well as in the absence of catalysts is described in this paper. The influence of the catalysts on the yield of the generated products is verified through a fractionation method based on relative solubility parameters. The influence of the catalysts on the conversion yield was also verified. The catalysts that yields the greater quantity of oils is the non-zeolitic aluminosilicate. However, in the overall conversion process of sugar cane bagasse, the most efficient catalyst was found to be zeolite A.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 7. CATALYTIC LIQUEFACTION IN MONOETHANOLAMINE (MEA) AND PRELIMINARY FRACTIONATION OF THE OBTAINED PRODUCTS

ABSTRACT

The liquefaction of sugar cane bagasse in monoethanolamine (MEA) in the presence of catalysts (zeolite A, non-zeolitic aluminosilicate and zinc chloride) as well as in the absence of catalysts is described in this paper. The influence of the catalysts on the yield of the generated products is verified through a fractionation method based on relative solubility parameters. The influence of the catalysts on the conversion yield was also verified. The catalysts that yields the greater quantity of oils is the non-zeolitic aluminosilicate. However, in the overall conversion process of sugar cane bagasse, the most efficient catalyst was found to be zeolite A.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 3. CHEMICAL CHARACTERIZATION OF THE PRODUCTS OBTAINED FROM THE CATALYTIC LIQUEFACTION OF BAGASSE WITH MONOETHANOLAMINE

The products obtained from liquefaction of sugar cane bagasse with monoethanolamine were characterized using a variety of methods: elemental analysis and UV-visible, FTIR, H¹NMR and C¹³NMR spectrometries. The oils were separated by conventional solubility techniques and were further fractionated into eight fractions (saturated, monoaromatic, diaromatic, triaromatic and poliaromatic hydrocarbons, resins, asphaltenes and pre-asphaltenes). These fractions were characterized by capillary gas cromatograpy with flame ionization detection and gas chromatography/mass spectrometry. Data obtained from simulated distillation of the oils provided useful information regarding product quality.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES. 1. LIQUEFACTION IN NON-HYDROCARBON SOLVENTS

Sugar cane bagasse is liquefied in the presence of various solvents under different experimental conditions. A series of ethanol amines (MEA, DEA, TEA), ethanol, ammonia and water are investigated as vehicles for the conversion, with tetralin being used as a reference solvent. The best results are obtained using ethanol amines. The influence of particle size, temperature, pressure and reaction time on the conversion yield, as well as on the product quality, are evaluated. Longer conversion times at high temperature not only increase the amount of liquefied product but also promote better upgrading to smaller molecules of immediate interest. The quality of the conversion products was followed by liquid column chromatography, permitting optimizing the liquefaction through product characterization.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES.2. CATALYTIC EFFECTS OF INORGANIC SALTS ON THE LIQUEFACTION OF BAGASSE WITH MONOETHANOLAMINE

Sugar cane bagasse was hydrogenated with monoethanolamine at 370°C under 2000psi of H₂ for 1h using different catalysts (metallic and zeolitic). The qualitative and quantitative aspects are compared through conversion yields and thermogravimetric and elemental analysis of the liquefield products.     

UPGRADING OF SUGAR CANE BAGASSE BY THERMAL PROCESSES.2. CATALYTIC EFFECTS OF INORGANIC SALTS ON THE LIQUEFACTION OF BAGASSE WITH MONOETHANOLAMINE

Abstract

Sugar cane bagasse was hydrogenated with monoethanolamine at 370°C under 2000psi of H₂ for 1h using different catalysts (metallic and zeolitic). The qualitative and quantitative aspects are compared through conversion yields and thermogravimetric and elemental analysis of the liquefield products.     

蔗糖企业机械设备用油(脂)的调查研究

对广西蔗糖行业的用油(脂)状况进行调查，发现传统的设备和润滑管理模式已不适应现代化糖厂的要求，应根据设备实际用油(脂)状况，通过采取技术改进和正确选用相应油脂等措施，提高设备润滑水平。     

煤液化油基本物理性质测定方法的研究

详细分析了煤液化油的两种切割方法（实沸点蒸馏法和气相色谱模拟蒸馏法）的原理和操作过程,重点探讨了各窄馏分的平均相对分子质量、表面张力、密度、黏度等物理性质及其多种测定方法和关联式法,从中选择出适合于测定煤液化油馏分这些物理性质的最佳方法：切割煤液化油采用实沸点蒸馏法,测定相对分子质量选用冰点下降法,测定表面张力使用FaceCBVP-A3自动表面张力仪,测量密度和黏度分别以比重瓶法和玻璃毛细管黏度法为宜,进而通过各馏分的性质预测煤液化油全馏分的物理性质。     

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.     

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。     

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.     

神华煤直接液化循环溶剂的催化加氢

采用百万吨级神华煤直接液化示范装置加氢稳定单元进料为加氢原料,在处理量300 mL加氢实验装置上考察了反应温度对煤直接液化循环溶剂性质的影响,并采用0.5 L搅拌式高压釜研究了煤在不同加氢深度循环溶剂中的液化效果。结果表明,随着溶剂加氢反应温度的升高,循环溶剂的硫、氮含量逐渐降低,氢/碳原子比增加;加氢反应温度由340℃升至380℃时,循环溶剂的芳碳率（f_a）不断减小,供氢指数（PDQI）逐渐增大,供氢能力增强。采用380℃加氢反应的循环溶剂进行煤液化时,煤的转化率和油收率均达到最大值,分别为88.64％和57.63％。当溶剂加氢反应温度达到390℃时,循环溶剂的供氢指数出现降低,芳碳率增加,供氢能力减弱,煤在此溶剂中加氢液化的转化率和油收率均有所降低,分别为88.22％和55.17％。     

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。     

碳纳米管负载NiMoP催化剂在煤直接液化油加氢中的催化性能

为考察碳纳米管(CNTs)载体在煤直接液化油加氢中的应用,将经功能化处理后碳纳米管负载活性组分NiMoP,对其进行SEM、TEM、BET、FT-IR、XRD、TG-DSC等表征,并采用高压釜对碳纳米管负载 NiMoP催化剂与常规的γ-Al2O3负载NiMoP催化剂进行煤直接液化油催化加氢活性的比较。结果表明：碳纳米管经浓硝酸纯化后,表面嫁接上更多的亲水性官能团,杂质含量降低,活性组分均匀分布在碳纳米管外壁。在液化油催化加氢活性对比中,以碳纳米管作为载体制备的NiMoP/CHCNTs催化剂,反应的相对加氢脱氮率为126(设定以γ-Al2O3为载体NiMoP催化剂的加氢脱氮率为100),其加氢性能优于NiMoP/γ-Al2O3催化剂。