催化热解调控热解产物的研究进展

综述了煤和生物质催化裂解技术对热解产物的影响作用,分析了不同催化剂对热解气体和煤焦油的催化效果,对热解产物催化裂解技术进行了分析,展望了未来煤催化裂解的研究重点。     

Pyrolysis studies of organic oxygenates. 2. Benzyl phenyl ether pyrolysis under batch autoclave conditions

Benzyl phenyl ether (BPE) is a reactive organic oxygenate which contains the ether functionality believed to be present in subbituminous and bituminous coals. With an $\text{H}\text{C}$ of 0.92 it has a $\text{hydrogen}\text{carbon}$ ratio similar to that found in bituminous coals. Benzyl phenyl ether reacts readily at 375 °C either in the presence or absence of added donor hydrogen sources. The major products are toluene and phenol. Other, heavier products are also produced in significant quantities. In general, as available donor hydrogen is reduced, the products tend to have higher molecular weights. Conventional pyrolysis products become lighter (more desirable) materials when the pyrolysis is carried out in the presence of added hydrogen.     

Coal flash pyrolysis: 5. Pyrolysis in an atmosphere of methane

Flash pyrolysis of coal at temperatures above 700°C and in the presence of methane produces substantially more ethylene and other low molecular weight hydrocarbons than are produced by pyrolysis of coal in the presence of nitrogen alone. Evidence is presented to show that the increase is due to pyrolysis of the methane quite independently of the coal, except with the possible catalysis by the coal, coke or mineral matter in the coal ash. This is contrary to recent reports in the literature.     

相转移催化合成芳基烷基醚

报道了以四丁基溴化铵为相转移催化剂，简便地合成了１０个芳基烷基醚，反应几乎是定量地快速进行。     

煤热解制焦油的工艺研究进展

煤热解是一种重要的煤炭分质利用技术,中低温热解焦油是制取液体燃料和化学品的重要原料。本文从对煤进行预处理、改变热解气氛、催化热解与催化加氢热解、煤与其它物质共热解、新型耦合热解工艺等方面综述了煤热解制焦油的工艺研究进展,探讨了影响煤热解过程焦油产率的因素及机理,并对各工艺进行了评价。     

Pyrolysis/g.c. of oil shales and coal

Pyrolysis studies of coal, kerogen and oil shales were carried out in a microprobe connected to a gas Chromatograph, in the temperature range 620–1160 °C. It was shown that the CO₂ evolved in the decomposition of the carbonates in the shales participates in the reaction and complete volatilization of the organic matter takes place. The product distribution can also be changed by the use of a nickel catalyst in the pyrolytic tube.     

Pyrolysis of naphthalenic derivatives: 3. Pyrolysis of naphthols,hydronaphthols and perhydronaphthols

Naphthols, hydronaphthols and perhydronaphthols, which are present in the acidic fraction of low-temperature tars and coal hydrogenates, have been pyrolysed between 993–1173 K. The thermal-degradation of 1-naphthol leads to naphthalene and indene; 2-naphthol produces only indene. The reaction pathways are similar to those of mononuclear phenols and dihydroxynaphthalenes. In the pyrolysis of tetralols, presumed intermediates of naphthol hydrogenation, the position of the hydroxyl group on the saturated ring or on the aromatic ring influences drastically the mechanism of degradation which consists mainly of decarbonylation and dehydroxylation. The thermal degradation of 1-decalol occurs mainly through the complete breakage of the molecule, allowing the formation of significant yields of monocyclic aromatics as in the cracking of decalin. The result obtained in this study further demonstrates the need for total hydrogenation of coal-derived oil for maximum production of benzene, toluene and xylene.     

东胜煤非等温热解特性与动力学参数确定

采用热重法考察了升温速率对高挥发分弱黏结性东胜煤热解特性的影响,结果表明:煤热解的3个阶段特征明显,最大失重速率温度(Tp)介于430℃￣480℃之间,由回归方程得到Tp和升温速率Ф之间的关系式为:Tp=1.124 4Ф+426.95;并采用非等温热重法对东胜煤的热解动力学参数进行了计算,结果表明其热解动力学参数能很好地反映煤的热解状况,东胜煤的反应级数确定为3。     

热等离子体裂解煤研究综述

本文论述了热等离子体裂解煤研究的产生背景、开发应用前景和重要性 ;分析了研究现状 ,指出气态等离子体 -固体颗粒两相流反应体系的基础性研究为今后的重点     

Pyrolysis—gas chromatography of Australian coals. 2. Bituminous coals

Pyrolysis—gas chromatography (Py—g.c.) was used to characterize quantitatively a series of high- to low-volatile bituminous Permian Australian coals. The levels of n-alkanes, n-alkenes and triterpenoids released by pyrolysis all decrease as a function of increasing rank and thus, the coal samples can be classified into three distinct groups. Carbon Preference Indices (CPI's) for alkanes and alkene/alkane ratios also decrease as a function of rank. The triterpenoids have exclusively the hopane skeleton. The hopane isomeric distributions exemplify the geological maturity of bituminous coals relative to brown coal (lignite). A significant correlation has been established between the level of n-alkanes and n-alkenes released under Py-g.c. conditions and the predicted oil yield by pyrolysis of these coals. Further development and application of the techniqueshould enable much to be learnt relating to the quality and yield of flash pyrolysis tars as well as the original coal macromolecular structure.     

二次反应对煤热解产品组成的影响

煤的热妥是煤炭转化过程中的第一步，通过热解可以产生高质量的热解煤气及珍贵的液体产品。然而在实际过程中，对热解产品的组成有不同的要求。因此，研究煤热解二次反应对实际过程有着重要的指导意义。     

煤在等离子体中热解直接生产乙炔

煤在富氢热等离子体中热解直接制取乙炔，是一条具有潜在工业发展前景的新工艺路线。最近发表的该技术的技术经济评价报告表明：等离子体热解煤直接制乙炔的生产成本与传统的水解电石法的乙炔成本基本相同，但新技术对环境没有污染，新技术的经济可行性在很大程度上取决于乙炔的最大收率及单位体积乙块的能耗，而这两个指标又由工艺条件（等离子体发生器和煤热解反应器的结构及氢气源成本等）和煤的性质决定。本文对国外在这一领域的工作进行了全面的评述，并扼要介绍了我们自己的研究工作。     

煤在还原性气氛下热解硫的析出机理研究进展

对煤在还原性气氛下热解硫的析出机理的研究进行综述,着重介绍了在氢气气氛下、焦炉气气氛下的脱硫机理及脱硫效果;并指出煤在甲烷气氛下热解,甲烷对脱硫存在促进作用。比较几种还原性气氛下煤热解的脱硫优缺点,指出甲烷对促进煤热解脱硫具有重要的研究价值和实际应用前景。     

Pyrolysis—gas chromatography of Australian coals. 1. Victorian brown coal lithotypes

Pyrolysis—gas chromatography (Py—g.c.) has been shown to be a useful technique for characterizing Victorian brown coal lithotypes. The pyrograms show marked changes in the predominance and distribution of specific molecular classes as a function of lithotype. Hydrogen-rich triterpenoid components are predominantly associated with the lighter lithotypes, whereas hydrogen-deficient phenolic components are more abundant in pyrolysates from the darker lithotypes. Carbon preference indices (CPIs) are >1 for the alkanes but <1 for the alkenes released by pyrolysis. All CPI values generally increase with darkening lithotype. Correlations of the components released with the maceral composition of the lithotypes have also been established. This information is used to establish some details of the mechanism of pyrolysis and the probable relative liquefaction behaviour of these lithotype samples.     

Anodic behaviour of unsaturated systems—I. Oxidation of some enol ethers: alkyl (aryl) oxy-3 propenonitriles

Enol ethers corresponding to the title compounds are oxidized at a platinum or glassy carbon anode in acetonitrile. In poorly nucleophilic media, the electrochemical reaction principally leads to dimers and oligomers due to the electrophilic attack of transient cations on the aromatic substituents of the ethylenic double bond. On the other hand, in the presence of efficient nucleophiles, the anodic reaction may appear to be more selective (at least in certain cases) and the product distribution demonstrates the formation of an intermediate epoxonium ion after the transfer of two electrons. In all media, reactions are furthermore discussed according to the nature of the substituents of the enol ether double bond.     

低变质粉煤成型热解的研究

以陕北低变质粉煤为原料,采用冷压成型制备型煤,主要研究焦煤添加量、添加水分、成型压力、热解温度的影响。结果表明:以焦煤作粘结剂进行型煤热解实验的研究中,可发现型煤(型焦)的抗压强度均随着焦煤加入量的增大而升高,选用10%的焦煤较为适宜;在一定范围内,型煤的强度随着成型压力的增大而增大,选择60kN的强度较为适宜;型煤的强度随着成型压力的增大而增大,14%的水分更佳;型焦的强度在700℃以上就趋于平稳化,故选择的热解温度为700℃。     

日本的煤炭快速热解技术

为了开发独具特色的煤炭快速热解技术,日本先后建立了原料煤处理量分别为7t/d和100t/d的工艺开发和中间试验装置。大量的试验研究结果表明：1t高挥发分原料煤经过快速热解,大致可以得到低热值的17．87MJ/m^3的煤气1000m^3,半焦250kg、焦油70kg、苯类（主要是苯、甲苯及二甲苯）35kg,同时还可副产水蒸气约300kg。目前,中试研究仍在进行中。     

浅谈煤样格金低温干馏应注意的问题

煤炭燃烧之前在较温和的条件下从高挥发分的煤中提取部分液体燃料和精细化学品具有重要意义。实验室格金低温干馏是考量这一性能的重要标准。文章从实验室化验条件出发,详尽阐述该实验项目中需要注意的问题,并着重分析如何较快较准确的判断实验过程中电极炭的添加量。     

Pyrolysis of hydrocarbon mixtures characteristic of coal: Application to dibenzyl mixture

Thermal cracking of dibenzyl dissolved in two solvents, tetralin and decalin, has been studied in a flow reactor, in the presence of steam, under atmospheric pressure and at temperatures between 600 and 750 °C. The nature of the products obtained depends upon the structure of the hydrogen-donor agent, but is independent of the structure of dibenzyl. Valuable products such as ethylene and a benzene, toluene and xylene (BTX) mixture, obtained by a β-scission reaction with a monomolecular mechanism, are predominant when decalin is used as solvent. The dehydrogenation of tetralin to naphthalene precedes cracking reactions of the bimolecular type, which lead to significant production of hydroaromatics such as indene. Cracking of dibenzyl, followed by hydrogen transfer from the solvent to the radicals formed, leads to toluene irrespective of the chemical nature of the hydrogen donor.     

采用热重法研究煤热分解反应动力学特性

采用热重法对煤热分解进行了大量实验研究，探讨了影响煤热分解的因素。由热分析结果确定了煤热分解反应动力学方程及其参数，并对热分解反应速度进行了探讨。