PRODUCTS FROM FLASH PYROLYSIS OF A TURKISH LIGNITE IN A FREE-FALL REACTOR UNDER VACUUM

Flash pyrolysis of a Turkish lignite under vacuum in a free-fall reactor was examined at a temperature range of 400 - 800 °C. Gaseous products were analysed with an on-line GC equipped with a manuel injection valve. Solvent fractionation was applied to the liquid product to separate preasphaltenes, asphaltenes and oils fractions. Two particle distributions of the lignite were used: -0.315+0.2 mm and -0.1 mm. The liquid yield increased with temperature up to 650 °C and, thereafter decreased for the larger particles. The maximum liquid yield, excluding pyroltic water, was found to be 8 % wt (dal) at 650 °C. In the case of the smaller particles the liquid yield increased steadily with temperature and the yield of liquid, excluding pyrolytic water, was 5.9 % wt (da) at 850 °C. The gaseous product yield also increased with temperature for both size fractions, and CO and CO₂ in the gaseous products were present in large amounts.     

DESULPHURIZATION OF A TURKISH LIGNITE BY PYROLYSIS COMPARISION OF SLOW AND FLASH PYROLYSIS

To observe the effect of the heating rate on the desulphurization. Bolu- Mengen lignite was desulphurized in the temperature range of 450-750 °C using flash and slow pyrolysis methods. A reduction of 57.6 % and 34.2 % In the total sulphur was obtained for the slow and flash pyrolysis at a pyrolysis temperature of 750 °C. respectively. It was observed that the flash pyrolysis is shifted toward higher temperatures with respect to the slow pyrolysis. The flash pyrolysis having high thermal efficiency has a potential as a desulphurization process.     

DESULPHURIZATION OF A TURKISH LIGNITE BY PYROLYSIS COMPARISION OF SLOW AND FLASH PYROLYSIS

ABSTRACT

To observe the effect of the heating rate on the desulphurization. Bolu- Mengen lignite was desulphurized in the temperature range of 450-750 °C using flash and slow pyrolysis methods. A reduction of 57.6 % and 34.2 % In the total sulphur was obtained for the slow and flash pyrolysis at a pyrolysis temperature of 750 °C. respectively. It was observed that the flash pyrolysis is shifted toward higher temperatures with respect to the slow pyrolysis. The flash pyrolysis having high thermal efficiency has a potential as a desulphurization process.     

微量元素Mo对褐煤有机质热解成烃的影响

有机-无机相互作用是沉积盆地内普遍存在且不可改变的事实。本文采用热模拟实验方法,论述了微量元素Mo对褐煤样品热解生烃产物的影响。结果发现：Mo元素的加入,增大了褐煤热解气态产物的产率,却降低了液态烃类的产率,同时,Mo元素对热解液态抽提物族组分的组成也产生了一定的影响,使产物中芳烃的产率有所减小,从而导致了饱芳比的增加。     

EFFECT OF PRESWELLING ON SOXHLET AND SUPERCRITICAL GAS EXTRACTION OF A TURKISH LIGNITE

Preswelling of Mugla-Yatagan lignite with THF (Tetrahydrofuran) followed by removal of the swelling agents results in higher extract yields, probably because the solvent molecules had easier access to the expanded pore structure of the swollen lignite. On the other hand, the yields of supercritical THF extract of the same lignite sample indicated that during removal of the swelling agent the expanded pore structure had collapsed. The results show that higher extract yields might have been obtained by the combined effect of the expanded pore structure of the swollen lignite and the solvent power of the mixed solvent,i.e., of the mixture of swelling agent and supercritical extraction fluid.     

热模拟实验中煤岩及显微组分饱和烃甾烷系列化合物有机地球化学特征

通过对塔里木盆地煤岩与壳质组的热模拟实验产物饱和烃进行色-质分析指出，在全煤和壳质组中检测出了丰富的甾族系列化合物，且以C₂₉甾烷占优势；煤岩中异常高的αββ构型异构化甾烷的检出反映了该煤在成岩早期经受过微生物改造；利用C_29-5αββ/(αα+ββ)与C₂₉ααα20S/(20S+20R)关系可以判识原油是否为未熟或成熟。孕甾烷/甾烷值与温度之间的关系表明孕甾烷可能不是甾烷的热降解产物；热模拟中Σ重排甾烷/Σ甾烷值在400℃开始降低和C₂₉αα20R/C₂₇αα20R值在400℃达到最大反映了甾烷骨架在该温度点以后发生开环裂解效应。     

CONTINUOUS HYDROGENATION OF FLASH PYROLYSIS COAL TAR

High melting tars from the flash pyrolysis of Millmerran coal have been upgraded to mobile liquid products by continuous hydrogenation over a fluidized nickel molybdate catalyst. The hydrogenation unit developed specifically for this purpose la described and changes In properties of the tar during hydrogenation are discussed.     

CONTINUOUS HYDROGENATION OF FLASH PYROLYSIS COAL TAR

ABSTRACT

High melting tars from the flash pyrolysis of Millmerran coal have been upgraded to mobile liquid products by continuous hydrogenation over a fluidized nickel molybdate catalyst. The hydrogenation unit developed specifically for this purpose la described and changes In properties of the tar during hydrogenation are discussed.     

塔里木盆地煤岩在不同介质条件下热模拟实验中烷烃系列有机地球化学特征

对塔里木盆地侏罗系煤岩在不同介质下的热模拟实验和正构烷烃系列色质测试分析结果表明,在400℃前后煤岩成烃机理不同。结合对峰型、ΣC21-/ΣC22+值、OEP指数和P r/Ph值等地球化学参数的研究,指出了不同热演化阶段的成烃机理:在低温阶段(<350℃)煤岩主要是裂隙、晶格间吸附烃和结构边缘烃的排出;在350~400℃之间,脱甲基及链断裂效应使得煤岩排烃进入高峰期;在高演化阶段(≥450℃),大量内部结构烃发生断裂重排,550℃以上温度达到第二个热降解高峰,产出烃发生脱甲基、链断裂和开环效应。模拟实验还表明,OEP指数变化较大,其每次变化都伴随一次生烃高峰;P r/Ph值随着热演化程度呈降低趋势;有水、伊利石和蒙脱石存在时,会改变煤岩在热演化过程中高碳数烃的热降解速率,有利于液态烃的形成。     

UPGRADING OF PETROLEUM RESIDUES BY VACUUM PYROLYSIS

ABSTRACT

Vacuum pyrolysis of petroleum residues which are classified as hazardous materials was performed in a batch reactor and enabled us to separate an upgraded oil from water and residual solids. Conversion of petroleum wastes to reusable oils reached 85% on an organic basis.

The pyrolysis oils and solid products were analysed for maltene, asphaltene and sulfur content. We found a significant increase in the pyrolysis oil maltene content. Much less sulfur was detected in the pyrolysis oil compared with the original organic waste material. The resin content of the pyrolysis oil decreased and the aliphatic, alicyclic and monoaromatic hydrocarbon content increased. The heavy portion of the pyrolysis oil contained approximately 5% of undesirable n-alkenes ranging from n-C₁₄ to n-C₃₈. Only trace amounts of organic and inorganic contamination was found in the solid phase leachate. The aqueous phase contained a small quantity of soluble organics which will be easily removed in a standard refinery water treatment plant. Results showed the merits of vacuum pyrolysis for upgrading petroleum residues.     

EFFECTS OF HEATING RATE AND PARTICLE SIZE ON THE PRODUCTS YIELDS FROM RAPID PYROLYSIS OF BEECH-WOOD

ABSTRACT

Effects of pyrolysis temperature (300–1000 ^°C), heating rates (100, 500, 1000, and 10,000 ^°C/s), and particle sizes (53–63,104–120,177–270, and 270–500 urn) on the yields and formation rates of tar, light oils, total gases, and char from pyrolysis of beech-wood under 1 atm helium pressure were studied. Wood particles were pyrolyzed in strips of stainless steel wire mesh in a captive sample apparatus; and yields of products were measured in weight percent of original wood as a function of temperature for different heating rates and particle sizes. The overall weight loss achieved from pyrolysis of this wood was about 90%. The total yields of tar and light oils from pyrolysis of this wood accounted for up to 80% of the original wood above 400 ^°C. Due to the post-pyrolysis reactions of tar and light oils, the tar and light oils yields go through a maximum with pyrolysis temperature for all particle sizes and most heating rates studied here. As particle size increases from 53–63 μm to 270–500 μm the maximum tar yield decreases from 53% to about 38%. The maximum tar yield also decreases with increasing the heating rate from 70% at 100 ^°C/s to 48% at 10,000 ^°C/s heating rate. Theses results indicate that as the intra-panicle post-pyrolysis cracking reactions of tar increases at higher heating rates and with larger particles the tar yield decreases. Tar was also analyzed with GPC for the effects of above pyrolysis parameters on the tar molecular weight. The tar average molecular weight. remains relatively constant (M_w = 300 amu, M_n = 155 amu, and M_z = 483 amu) under helium atmosphere with pyrolysis temperature at 1000 ^°C/s heating rate and with 53/63 u m particle size. The average molecular weight of tar does not significantly varies with heaung rate, but it decreases as the particle size increases.     

减压渣油在柱形超声聚能反应器中的改质降黏

 设计和开发了柱形超声聚能反应器,研究了超声波输出电压、作用方式、作用时间、作用温度对减压渣油改质降黏的影响,还对超声波处理后渣油黏度的恢复、凝点下降和<500℃轻组分体积分数的变化进行了分析。结果表明,超声连续辐照比脉冲辐照对减压渣油改质的降黏效果好;减压渣油黏度随超声波输出电压、作用时间的延长和温度的提高而下降。在20kHz超声波的输出电压250V、温度180℃、时间60min的条件下,减压渣油40℃黏度的降黏率为26.8％,在40℃静置5d后其降黏率仍为24.4％,减压渣油中<500℃轻组分的体积分数增加了1.0％,凝点下降了1℃。     

EFFECTS OF HEATING RATE AND PARTICLE SIZE ON THE PRODUCTS YIELDS FROM RAPID PYROLYSIS OF BEECH-WOOD

Effects of pyrolysis temperature (300-1000 ^°C), heating rates (100, 500, 1000, and 10,000 ^°C/s), and particle sizes (53-63,104-120,177-270, and 270-500 urn) on the yields and formation rates of tar, light oils, total gases, and char from pyrolysis of beech-wood under 1 atm helium pressure were studied. Wood particles were pyrolyzed in strips of stainless steel wire mesh in a captive sample apparatus; and yields of products were measured in weight percent of original wood as a function of temperature for different heating rates and particle sizes. The overall weight loss achieved from pyrolysis of this wood was about 90%. The total yields of tar and light oils from pyrolysis of this wood accounted for up to 80% of the original wood above 400 ^°C. Due to the post-pyrolysis reactions of tar and light oils, the tar and light oils yields go through a maximum with pyrolysis temperature for all particle sizes and most heating rates studied here. As particle size increases from 53-63 μm to 270-500 μm the maximum tar yield decreases from 53% to about 38%. The maximum tar yield also decreases with increasing the heating rate from 70% at 100 ^°C/s to 48% at 10,000 ^°C/s heating rate. Theses results indicate that as the intra-panicle post-pyrolysis cracking reactions of tar increases at higher heating rates and with larger particles the tar yield decreases. Tar was also analyzed with GPC for the effects of above pyrolysis parameters on the tar molecular weight. The tar average molecular weight. remains relatively constant (M     

CHARACTERIZATION OF COAL CHARS FROM A FLASH PYROLYSIS PROCESS BY CROSS POLARIZATION/MAGIC ANGLE SPINNING 13C NMR

Chars from the Illinois Springfield (No. 5) Coal are prepared by flash pyrolysis at progressively higher charring temperatures. The results of a study of these chars by ¹³C NMR with CP/MAS indicate that the initial stage of heating (300^°C) produces a char with aromatic carbon fraction (f_ar) of 68%, and successive heating gives chars with f_ar of 70% (400^°C), 73% (500^°C), 89% (600^°C), 95% (700^°C), and 96% (800^°C). However, the actual amount of aromatic and aliphatic carbon in the char can be calculated by using the NMR measurements, the organic carbon content of the char, and the weight of the char. The calculated values show that the amount of aromatic carbon in char remains relatively constant at each temperature, but the amount of aliphatic carbon in char is reduced during higher temperature charring. At 600^°C, both a large reduction of the aliphatic carbon content and a maximum weight loss occur. Evidently, the aliphatic-bond carbon in coal is the principal source of volatiles derived from coal. The apparent increase in aromaticity (f_ar) of the char heated to progressively higher temperatures is due to the loss of aliphatic-bond moieties and reduction in volume of materials.     

CHARACTERIZATION OF COAL CHARS FROM A FLASH PYROLYSIS PROCESS BY CROSS POLARIZATION/MAGIC ANGLE SPINNING 13C NMR

ABSTRACT

Chars from the Illinois Springfield (No. 5) Coal are prepared by flash pyrolysis at progressively higher charring temperatures. The results of a study of these chars by ¹³C NMR with CP/MAS indicate that the initial stage of heating (300^°C) produces a char with aromatic carbon fraction (f_ar) of 68%, and successive heating gives chars with f_ar of 70% (400^°C), 73% (500^°C), 89% (600^°C), 95% (700^°C), and 96% (800^°C). However, the actual amount of aromatic and aliphatic carbon in the char can be calculated by using the NMR measurements, the organic carbon content of the char, and the weight of the char. The calculated values show that the amount of aromatic carbon in char remains relatively constant at each temperature, but the amount of aliphatic carbon in char is reduced during higher temperature charring. At 600^°C, both a large reduction of the aliphatic carbon content and a maximum weight loss occur. Evidently, the aliphatic-bond carbon in coal is the principal source of volatiles derived from coal. The apparent increase in aromaticity (f_ar) of the char heated to progressively higher temperatures is due to the loss of aliphatic-bond moieties and reduction in volume of materials.     

油页岩干酪根热解产物特性研究

采用裂解色谱(PY-GC-MS)、电子顺磁共振波谱(EPR)和红外光谱(FTIR)等技术手段,分析了Estonia油页岩中干酪根及其热解产物的结构特性,研究了不同温度下中间产物与最终产物的关联性.结果显示:油页岩热解符合干酪根热解为中间产物热沥青,热沥青再热解为页岩油、干馏气和半焦等产物反应路径,中间产物热沥青的生成趋...     

LOW TEMPERATURE PYROLYSIS OF BLACK LIQUOR AND POLYMERIZATION OF PRODUCTS IN ALKALI AQUEOUS MEDIUM

ABSTRACT

Atmospheric pressure pyrolysis for the production of liquids and gases from black liquor and its calcium salts and acidic precipitate have been carried out in a little stainless steel tube. Yields, sum of liquid and gas products, from black liquor and its calcium salts and acidic precipitate were 44.7 %, 52.0 % and 59.1 % of dry basis respectively. The precipitates obtained from black liquor by acidifying with hydrochloric acid and passing carbon dioxide have been polymerized in aqueous acetone containing formaldehyde and ammonia, and converted a polymeric resin.     

塔河减压渣油浆态床加氢改质反应条件的考察

以塔河减压渣油为研究对象,通过高压釜反应模拟浆态床加氢反应过程,考察反应条件对塔河减压渣油加氢转化过程生焦率、转化率及产物分布的影响。结果表明,随反应温度的升高,渣油转化率及生焦随之增加;氢初压的提高对生焦有明显的抑制作用,起初渣油转化率随之降低,当超过8 MPa时略有增加;反应时间的增加对渣油转化率及生焦都有促进作用;催化剂的存在可以抑制生焦反应,同时在一定程度上也抑制了裂化反应,应控制适量。综合考虑,确定适宜的反应条件为：反应温度不宜高于430 ℃,氢初压7～8 MPa;反应时间40～60 min;催化剂的加入量2 000～6 000 mg/kg。     

LOW TEMPERATURE PYROLYSIS OF BLACK LIQUOR AND POLYMERIZATION OF PRODUCTS IN ALKALI AQUEOUS MEDIUM

Atmospheric pressure pyrolysis for the production of liquids and gases from black liquor and its calcium salts and acidic precipitate have been carried out in a little stainless steel tube. Yields, sum of liquid and gas products, from black liquor and its calcium salts and acidic precipitate were 44.7 %, 52.0 % and 59.1 % of dry basis respectively. The precipitates obtained from black liquor by acidifying with hydrochloric acid and passing carbon dioxide have been polymerized in aqueous acetone containing formaldehyde and ammonia, and converted a polymeric resin.     

在多室环流反应器中用FCC干气制备乙醛

在多室环流反应器(MALR)中用模拟和真实的催化裂化干气制备了乙醛，考察了反应温度、反应压力、原料气中乙烯浓度和催化剂溶液中钯离子(Pb^2 )浓度对乙烯的单程转化率和乙醛选择性的影响。结果表明，在多室环流反应器中用FCC干气制备乙醛的适宜条件为：反应温度100～120℃，反应压力0．5～0．6MPa，催化剂溶液中Pb^2 质量浓度为0．6～0．9g／l。