Hydrogenation of Bituminous Sand

The effect of the conditions of bituminous sand hydrogenation on the yields and properties of the resulting liquid hydrocarbons was studied. It was found that, on the hydrogenation of bituminous sand, hydrocarbon products of higher quality can be obtained with a higher yield, as compared with the products of pyrolysis. The conditions affording a maximum yield of synthetic oil or an increased yield of light hydrocarbons were determined.     

Characterization by pyrolysis-gas chromatography-mass spectrometry of the insoluble organic residues derived from the hydrogenation of Tasmanites sp. oil shale

The insoluble organic residues from the hydrogenation of Tasmanites sp. oil shale have been characterized by Curie point pyrolysis combined with gas chromatography and computerized gas chromatography-mass spectrometry. The resulting pyrograms show that very little, if any, hydrogenation of the residues occurs. Rather, the initial step in the sequence is pyrolysis of the residue followed by hydrogenation of the liquid products. Major compounds identified from the pyrograms of the residues include alkene/alkane doublets, mixtures of diterpenoids and mono- di- and triaromatic compounds. Changes in the distribution of these compounds with changes in reaction conditions are discussed.     

Using the spent alumina catalysts of methyl phenyl carbinol dehydration

To assess the possibility of using spent alumina catalysts from the vapor-phase dehydration of methyl phenyl carbinol as a support of fixed-bed catalysts, we determined the textural changes and mechanical strength of the catalyst over its scheduled service life of 8000 h. It was found that the catalytic properties of a palladium catalyst prepared on this support (0.2 wt % Pd) in reactions of hydrogenation and polymerization of diene hydrocarbons in liquid pyrolysis products are as good as the commercial products APKGS-20 E2 and APKGS-20 Sh. The tested catalyst is recommended as a replacement for the inert attachment in reactors for the hydrostabilization of liquid pyrolysis products.     

Kinetic relationship of coal hydrogenation,pyrolysis and dissolution

Data are presented concerning the production of gaseous and liquid products from coal. The processes considered include pyrolysis, dissolution in solvent with and without the application of ultrasonic energy, batch hydrogenation, and continuous hydrogenation. The products are compared with respect to both quantity and type. Activation energies are presented and mechanisms discussed. Coal hydrogenation in the presence of an appropriate catalyst shows very great promise as a means of converting coal to liquid and gaseous fuels. Yields of 30% high octane gasoline, 5% diesel oil, 35% high Btu gas, and 30% char, on a weight basis, have been achieved.     

喷动-载流床中Co/ZSM-5分子筛催化剂对煤热解的催化作用

在喷动-载流床中考察了Co/ZSM-5分子筛催化剂对煤热解气、液、固产物产率及组成变化的影响,分析了催化剂失活的原因及催化剂的再生使用寿命. 结果表明,在550~600℃的热解温度范围内,Co/ZSM-5分子筛催化剂提高煤热解总转化率达70%以上. 而在650℃时,煤热解正己烷可溶物产率最大,其中酚类、脂肪烃类和芳香烃类的产率比无催化剂时分别增加203%, 51%和78%. 因积碳失活的Co/ZSM-5分子筛催化剂经过500℃焙烧后再生使用6次,活性下降不到5%. Co/ZSM-5分子筛催化剂的结构表征结果说明,Co进入了ZSM-5分子筛骨架. Co的催化加氢活性促进了H·与煤热解焦油片断的结合,减少了焦油聚合成大分子的几率,从而提高了煤热解油品的产率和品质.     

Co-pyrolysis as a method of upgrading some products of coal processing

Co-pyrolysis was investigated as a method of upgrading various products resulting from coal processing. Co-pyrolysis of vacuum residue (VR) with coal extraction products as well as with primary tars from flash pyrolysis leads to a considerably enhanced yield of liquid products. It has been established that superheated steam and increased outgassing rate, favour the yield of liquid products. The proportion of the ingredients in the mixture as well as the quality of the VR also have a definite effect. The excess yield of liquid products in co-pyrolysis of coal extraction products was 8–23 wt%, depending on operating conditions and the composition of the mixture. The flash co-pyrolysis of primary tars yielded a 1.5–15.9 wt% surplus of liquid products depending on the mixture composition. Products originating from co-pyrolysis of these raw materials with VR are characterized by relatively high atomic hydrogen to carbon ratio, usually not less than 1.5 and the total abscence of asphaltenes. Generally, co-pyrolysis of VR with various products of coal processing is comparable with hydrogenation in the light of good yields of liquid products.     

Formation of porous structure of semicokes from pyrolysis of Turkish coals in different atmospheres

Activated carbons were obtained from Turkish coals by one-step steam pyrolysis process. The effect of the water vapor on the yield of the solid, liquid and gas products was studied. The presence of steam during pyrolysis-activation process contributes to distillation of low molecular weight products and reacts with the coal and the volatile products obtained during the pyrolysis. These processes lead to an increase in the yield of liquid and gas products and a decrease in the solid yield. The resulting carbons are determined to have good adsorption characteristics.     

苯乙炔选择性加氢滴流床反应器内的液相轴向返混特性

苯乙炔选择性加氢是从裂解汽油C₈馏分中回收苯乙烯的关键反应,本文采用滴流床反应器对该反应体系的液相轴向返混行为进行了研究。首先利用脉冲示踪法测得了不同操作条件下的液相停留时间分布密度;然后基于固定床轴向扩散模型,通过有限元正交配置法和Levenberg-Marquardt非线性最小二乘法,计算得到了Péclet数和液相平均停留时间;最后考察了主要操作条件对液相轴向返混的影响。研究结果表明,增大液体流量、气体流量、温度以及压力均可减小液相返混,而增大颗粒粒径会使液相返混加剧。     

废轮胎热裂解技术研究现状与进展

结合目前废旧轮胎资源化处理现状及研究成果,本文对热解机理、热解技术进行分析、对比,着重介绍了热解温度、升温速率、物料粒径、催化剂等工艺参数对热解产物产率的影响,分析表明Coast-Redfern积分法所得动力学模型较准确,平均反应活化能为129.5kJ/mol;现有的研究表明,热解温度对产物产率影响最大,气相产物与液相产物产率随温度升高而增加,其中液相产物产率相对较高的热解温度在500～550℃范围内,固相产物品质较高的热解温度在500～650℃范围内。其次对其固、液、气三相产物特性及应用和污染物(S、PAHs)的分布与控制方法做了归纳总结,为废旧轮胎热解技术向工业化发展提供技术依据。     

Structures of the distillates obtained from hydrogenation and pyrolysis of Liddell coal

The structures of the distillable fractions (oils, b.p. >200 °C and volatile fractions, b.p. <200 °C) of the products from hydrogenation and pyrolysis of an Australian bituminous coal (Liddell) were investigated by gas chromatography-mass spectrometry (g.c.-m.s.) and nuclear magnetic resonance spectroscopy (n.m.r.). The distillable oil generated from hydrogenation of Liddell coal at 400 °C, using nickel molybdenum ortin (II) chloride as catalyst and tetralin or recycle oil as vehicle, consisted of a wide range of compounds. Long straight-chain alkanes were important components together with alkyl-substituted benzenes and tetralins, phenols and polycyclic material. When yields were low, as in the case of catalytic experiments with nickel molybdenum catalysts and no vehicle, isoprenoids could be identified. When a substantial proportion of the coal was converted to oil, branched-chain alkanes were not important components of the product. The replacement of tetralin and nickel molybdenum catalyst with stannous chloride reduced the amounts of methyl tetralins in the product. When tetralin was replaced by recycle oil, alkanes were more important components of the liquid products. Although alkenes were absent in oils generated by hydrogenation, they were important components of oils generated by pyrolysis. The highly volatile fractions (b.p. <200 °C) produced during hydrogenation consisted of alkyl-substituted benzenes, decalins, methylindan and straight-chain alkanes. Straight-chain alkanes were more abundant in those volatile fractions generated by hydrogenation with recycle vehicle than with tetralin. The Brown-Ladner method of estimating the fraction of aromatic carbon in distillable oils was adequate for less volatile fractions but was inadequate for the highly volatile fractions because of the large amounts of α-CH₃ and β-CH₃ alkyl groups present.     

高粱秸秆热解产物的研究

研究了热解温度、气体流量、加热速率和保温时间三个操作因素对高粱秸秆热解产物(生物油和残炭)分布的影响。结果表明,对高粱秸秆热解产物的分布有很大影响的因素是热解温度和气体流速。在热解升温速率为10℃/min、热解温度为450℃,氮气流速为100mL/min、保温时间为1h的条件下,液体收率最高。     

Kinetik der Kohlen-Pyrolyse als Grundlage für die Auslegung technischer Reaktoren

Kinetics of coal pyrolysis as a foundation for the design of technical reactors . The pyrolysis of coal is understood to mean its thermal decomposition at temperatures above 300°C, affording tar and char. It is the basic process underlying coking and the starting reaction of combustion, gasification, and hydrogenation. In addition, pyrolysis offers a means of converting coal into gases and liquids in a ?third way”? besides gasification and hydrogenation. In order to establish a basis for the design of relevant technical reactors, the kinetics of coal pyrolysis has been investigated as a function of temperature and rate of heating and recently of pressure under inert gases and hydrogen. In particular, the rates of formation and the yields of liquid and gaseous products and the alteration of the solid matter have been examined under pressures ranging from 1 to 100 bar and at rates of heating between 0.05 and 1 000 K/s. It is shown how product formation can be controlled by these parameters and how the experimental data can be applied to reactor design.     

云南松热解及其热解产物的研究

采用自制固定床反应器对云南松木粉进行热解,探讨了热解温度、原料颗粒尺寸和氮气流速对云南松热解特性的影响,并采用GC-MS对生物油的组分含量进行分析。结果表明:在热解温度为500 ℃,原料颗粒尺寸为0.250~0.420 mm,氮气流速为150 mL/min条件下,生物油的产率最高为50%,液体组分主要以2,6-二叔丁基对甲酚、2-甲氧基-4-甲基苯酚、异丁香酚、愈创木酚为主,占液体总量的39.24%。     

木块微波裂解及产物组成分析

使用2 450 MHz/12 kW微波裂解装置裂解木块并对不同裂解条件下气、液产物进行了分析。结果表明,木块微波裂解生成了极具价值的生物油、合成气等产品;裂解功率对液体产品收率及主要组分的种类产生影响;裂解温度对液态产品各组分相对含量及气态产品的成分构成产生影响。     

玉米秆酶解残渣木质素热解实验研究

对玉米秆酶解残渣木质素进行热重分析,结果表明,木质素热裂解主要发生在180～500℃,综合考虑热解效率和液体产物产率最大化,选取快速热解实验的热解温度范围为500～600℃。并在实验室自行设计的装置上对木质素进行热解实验,在550℃时得到热解液体产物热解油最大产率,为30.9%。对热解油进行气相色谱―质谱分析,结果显示木质素热解产物相对简单,一级和二、三、四级热解油的成分主要是酮类和酚类;而电捕油中酮类很少,大部分是酚类,另有15.07%的2,3-二氢苯并呋喃。     

Process analysis of catalytic multi-stage hydropyrolysis of lignite

The process and the mechanism of multi-stage hydropyrolysis (MHyPy) of coal were investigated by analyzing the products of different MHyPy processes in detail. The results showed that the suitable holding temperature was near the peak temperature (350–500 °C) at which more free radicals were produced rapidly, thus more oil was formed and the hydrogen utilization efficiency was increased. The cleavage of organic functional groups in char from MHyPy was mostly affected by the pyrolysis temperature. The effect of retention was to change the product distribution through stabilization of the free radicals and hydrogenation of the heavier products. In the holding stage the specific surface area and average pore volume of the char were increased due to the escape of more hydrogenation products.     

Pyrolysis of lignin in coal-tar pitch

The pyrolysis of hydrolytic lignin in coal-tar pitch over a temperature range of 320–380°C was studied in a batch reactor at atmospheric pressure. As a result of reactions with pitch, lignin underwent dissolution and destruction with the formation of compounds that remained in the reactor or were released from the reactor as liquid and gaseous products. The liquid products of the pyrolysis of lignin consist of organic and aqueous phases. The organic products of the pyrolysis of lignin in pitch predominantly contain guaiacol and its derivatives. The chemical interaction of coal-tar pitch with lignin leads to changes in the characteristics of pitch, an increase in the softening point, an increase in the concentrations of compounds insoluble in toluene and quinoline, and an increased yield of the coke residue.     

水洗-烘焙联合预处理对稻壳微波热解产品特性的影响

预处理技术能提高生物质热解产物的品质。本文研究了水洗-烘焙联合预处理技术对稻壳微波热解的产物特性的影响,结果表明:水洗-烘焙联合预处理技术增加了固体产率,而减少了液体和气体的产率;联合预处理技术提高了稻壳微波热解气体产物的品质,气体产物中CO₂含量减少,CH₄和H₂的含量增加,气体产物的热值提高到13MJ/m³;联合预处理技术提高了稻壳微波热解液体产物的品质,增大了液体产物中苯酚类和糖类的含量,减少了液体产物中酸的含量,简化了液体产物的成分。     

喷动-载流床中粒径对内蒙霍林河褐煤快速热解产物的影响

在喷动–载流床内对霍林河褐煤进行了快速热解，考察了0.125~0.28 mm范围内煤粉颗粒粒径对煤热解总失重、热解产物产率以及气体和液体产物具体组成的影响. 气体和液体产物的组成分别利用气相色谱和色质联用仪分析. 实验表明, 随颗粒粒径增大，煤中挥发份脱出率略有降低，半焦产率略有升高，气体总产率增大，CH4，无机气体，C2H6，C3H8等呈现上升趋势. 而随颗粒粒径增大，液体产率降低，其中沥青质的降低较为显著. 正己烷可溶物产率随颗粒粒径增加有少许降低. 热解水产率随着颗粒粒径的增大而增加. 颗粒粒径对正己烷可溶物中的各类组份的含量也有一定的影响.     

皂脚酸化油的热裂解过程与产物分析

拟通过快速热裂解的工艺,得到燃料性能较优的气体和液体产物,从而提高废弃油脂的利用价值。本实验以皂脚酸化油为原料,对其热裂解过程进行研究,并对裂解产物进行分析。液体产物性能分别为：酸值78mg/g,黏度2.5mm2/s,密度0.83g/cm3,热值为41.9kJ/g。采用气质联用仪分析液体产物,表明热解产物中含有烷烃、烯烃、芳香烃、酮以及酸等组分,碳链长度主要分布在C10～C18。用气相色谱分析气体产物,表明气体主要为可燃气体,其中CO、H2、CH4、C2H6这4种气体含量就达到70%。实验结果表明,快速热裂解反应显著提高了皂脚酸化油的燃料性能：羧酸含量显著降低,燃烧热值增大,为皂脚的进一步深加工利用提供理论依据。