PROBABILISTIC MODELLING OF LIGNIN LIQUEFACTION

ABSTRACT

The results of the thermal and catalytic reactions of lignin model compounds are used in the a priori prediction of its liquefaction. Lignin was defined probabilistically as an ensemble of single ring aromatics with substituents on each of their six ring positions. Elements in a substituent vector x¹, for each ring position i, were matched into all possible combinations to describe lignin. Initial number fractions, or probabilities, for each vector element were ascertained through inspection of lignin structural data. The reaction of lignins altered the probabilities within each substituent vector, and reaction products were also calculated by matching all combinations of vector elements for each ring position. Model compound results provided the identities and rates of change of vector elements.

This simulation of lignin liquefaction predicted the yields of permanent gases, aqueous liquids, single- and two-ring phenolic products, and a carbonaceous residue. The impact of the distribution of oligomeric sizes on catalyst effectiveness was probed.     

MODELING LIGNIN LIQUEFACTION 1. CATALYTIC HYDROPROCESSING OF LIGNIN-RELATED METHOXYPHENOLS AND INTERAROMATIC UNIT LINKAGES

The reactions of two sets of lignin model compounds over a sulfided CoOMoO3/γ-Al2O3 catalyst were studied. The first set mimicked lignin methoxyphenol residues and comprised 4-methyl-guaiacol, 4-methyl catechol, eugenol and vanillin. Deoxygenation and hydrogenation were facile and led to ultimate molar yields of single-ring products as high as 0.70. The selectivity to single-ring products increased with increases in temperature, o-hydroxydiphenylmethane, phenyl ether and o,o'-biphenol constituted the second set that mimicked thermally stable lignin bonds.Fragmentation of o-hydroxydiphenylmethane and phenyl ether occurred readily; o,o'-biphenol reacted to dibenzofuran.

These results suggest that the single-ring products obtained from catalytic liquefaction of lignins should be more desirable than those obtained from pyrolysis because of both higher yields and reduced complexity.     

MODELING LIGNIN LIQUEFACTION 1. CATALYTIC HYDROPROCESSING OF LIGNIN-RELATED METHOXYPHENOLS AND INTERAROMATIC UNIT LINKAGES

ABSTRACT

The reactions of two sets of lignin model compounds over a sulfided CoOMoO3/γ-Al2O3 catalyst were studied. The first set mimicked lignin methoxyphenol residues and comprised 4-methyl-guaiacol, 4-methyl catechol, eugenol and vanillin. Deoxygenation and hydrogenation were facile and led to ultimate molar yields of single-ring products as high as 0.70. The selectivity to single-ring products increased with increases in temperature, o-hydroxydiphenylmethane, phenyl ether and o,o’-biphenol constituted the second set that mimicked thermally stable lignin bonds.Fragmentation of o-hydroxydiphenylmethane and phenyl ether occurred readily; o,o’-biphenol reacted to dibenzofuran.

These results suggest that the single-ring products obtained from catalytic liquefaction of lignins should be more desirable than those obtained from pyrolysis because of both higher yields and reduced complexity.     

木质素表面活性剂及木质素磺酸盐的化学改性方法

介绍了利用造纸工业的主要副产品木质素制取表面活性剂以及对木质素磺酸盐的几种有效的化学改性方法与产品应用途径 ,给出了用木质素改性制备水煤浆添加剂的实例。     

天然气液化工艺的选择

液化天然气在天然气的远洋运输，边远气田气体的利用以及城市燃气调峰中起到了重要的作用。本文概述了液化天然气的净化和液化工艺，对每种工艺的优缺点进行了分析比较，并指出了液化工艺的新的发展动向。另外，对新疆呼图壁、彩南、莫北三个油气田所产的天然气提出了液化方案。     

煤液化残渣加氢性能

通过含大量沥青质的煤液化残渣在微型反应釜的加氢实验,考察了温度、气氛、H2初压以及反应时间对煤液化残渣中油(Oil)、沥青质(PAA)和四氢呋喃不溶有机质(THFIS)加氢性能的影响.结果表明,煤液化残渣中的PAA和THFIS可进一步加氢转化成Oil,煤催化液化残渣与煤非催化液化残渣中的PAA最高转化率分别为77.43%和80.54%;N2压的存在能促进煤液化残渣中THFIS转化成PAA,高压H2有利于THFIS和PAA加氢转化成Oil.煤催化液化残渣和煤非催化液化残渣的最佳的加氢温度均为450℃,最佳的H2初压均为6 MPa,最优的反应时间分别为60 min和30 min.     

ELEMENTAL COMPOSITION OF ASPHALTENES FROM COAL LIQUEFACTION

The elemental composition (C, H, N, S, O) of asphaltenes isolated from coal liquefaction experiments carried out at different temperatures and tetralin/coal ratios has been determined. The liquefaction experiments were conducted in a 250 ml autoclave, with 10 g of a Spanish subbituminous A coal, for 1 hour, and at 17 ± 1 MPa operating pressure and 400 rpm stirring speed. The liquefaction products were fractionated into oils, asphaltenes and preasphaltenes using pentane, toluene and THF as extractive solvents. The % S and % O are lower in asphaltenes than in coal, while the % C and % N are higher and % H depends on the temperature and tetralin/coal ratio used. On the other hand asphaltenes % C decreases, and % H and % O increase as the tetralin/coal ratio is raised at every temperature except 475 °C, while % S and % N do not have a clear variation.     

��װʽ��Ȼ��Һ��װ�������뿪��

气田的边远地区存在着大量零散天然气资源，由于受地理环境所限，无法就地利用，敷设管道集气外输又很不经济；为此吉林油田、中国石油天然气总公司和中国科学院低温中心联合开发研制了５００ＬＮＧ橇装式工业实验装置进行回收利用。该装置设计天然气处理能力为６５０ｍ３／ｈ，采用分子筛深度脱水，同时脱二氧化碳；气轴承膨胀机氮气循环致冷回收ＬＮＧ工艺，设计ＬＮＧ产量为５００Ｌ／ｈ。该装置于１９９６年１２月整体试车成功，各项技术指标均达到或接近设计值，基本达到工业化生产条件。整个装置包括１０个橇块，全部设备国产化，水、电、燃料等全部自给。     

木粉在超临界甲醇中的液化研究

以木粉和甲醇为原料,在高压反应釜中进行木粉在超临界甲醇中的液化分解反应,研究甲醇与木粉的配比、反应时间、反应压力、催化剂种类及用量对木粉分解率、气化率和液化率的影响。结果表明,以NaOH为催化剂,在甲醇与木粉质量比为4.5、反应温度为320℃、反应时间为1h的条件下,木粉液化率达到43.3%。     

木质素醇醚非离子表面活性剂的合成及性能

以造纸废液中提取的碱木素为原料合成了木质素醇醚非离子表面活性剂。确定了由中间体木素醚合成产品的最佳工艺条件为 :醚醇摩尔比为 1∶ 1 .2 ,反应温度为 1 45℃ ,反应时间为 1 h。测定了产品的红外光谱 ,并对其表面活性、乳化性、增溶性、泡沫高度等进行了研究。     

火烧油层物理模拟的研究

火烧油层法有与蒸汽气采法不同的机理和特点，它作为常规稠油，超稠油开采方法的补充，目前在国内外油田现场正不断得到应用，相应的实验室技术－火烧物理模型及其应用研究也不怕加强。除介绍了火烧油层法的机理和特点外，主要介绍了火 物理模拟装置，火烧物理模拟相似准则及三大燃烧系数和其它物理模拟试验可得到的结果，如火烧经济指标等。     

KINETICS OF THERMAL LIQUEFACTION OF SEYITÖMER LIGNITE

Kinetics of non-catalytic liquefaction of Seyitomsr lignite has been investigated under hydrogen pressure, using tetralin as a Bolvent in a laboratory Bcale batch autoclave reactor.

In the first set of experiment hydrogen initial pressure and reaction temperature were kept constant, the reaction time and coal/aolvent ratio were changed at five and three levels espectively. In the second set of experiments coal/solvent ratio was kept constant and hydrogen initial pressure, reaction temperature and time were individually changed at four levels. The produot was analyzed in terms of total conversion, liquid yield and liquid product distribution determined as preasphaltenes, asphaltense and oila. A satisfactory correlation was obtained using the kinetic model proposed by Shalabi et al (1979).     

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%.     

煤液化残渣加氢性能研究

 通过含大量沥青质（PAA）的煤液化残渣（CLR）在微型反应釜的加氢试验,考察了温度、气氛、氢初压以及反应时间对CLR中油（Oil）、沥青质（PAA）和四氢呋喃不溶有机质（THFIS）加氢性能的影响。结果表明,CLR中的重质组分—PAA和残余煤可进一步加氢转化成Oil,CLR–A、B中PAA最高转化率分别为77.43%和80.54%;氮气压力的存在能促进CLR中残余煤转化成PAA,高压氢有利于残余煤和PAA加氢转化成Oil。试验得出,在本实验范围内CLR-A、B的适宜加氢温度均为450℃,最佳氢初压均为6 MPa,最优反应时间分别为60min、40min。     

煤炭直接液化油品加氢改质中试研究

 进行了煤直接液化油品的提质加工加氢改质工艺中试研究。中试装置规模为340kg/h进料,反应器绝热设计。结果表明,采用RGC-1/RNC-2/RCC-1催化剂组合,在高分压力约13.0MPa、精制反应器和改质反应器加权平均温度分别为351.3和362.6 ℃的反应条件下,几乎可以全部脱除煤直接液化油中的S、N、O等杂质,同时绝大部分二环以上芳烃被加氢饱和,加氢精制段对芳烃加氢饱和起主要作用。此外,对煤直接液化油品加氢改质试验进行了物料衡算,详尽分析了石脑油和柴油馏分性质,考察了添加十六烷值改进剂对加氢改质柴油馏分的作用。     

DIRECT LIQUEFACTION OF WOOD BY CATALYST AND WATER

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%.     

MANAGEMENT OF COAL MACERALS IN THE LIQUEFACTION OF LOW RANK COALS

ABSTRACT

Three Alberta subbituminous coals were selected to investigate the contribution of different macerals to liquefaction. These coals represent the full range of geographic, rank and geological variations present In the Alberta Plains Coal Region. In addition, for comparison, two U.S. lignites (Texas and North Dakota) were included in these investigations. To enhance maceral concentration, density fractionation was carried out on these samples. Though liquefaction yields appear to increase with increase in vitrinite (huminite) content, a clear-cut correlation between conversion and maceral content is not established because of (a) uncertain behaviour of semi-inert macerals and (b) differences in behaviour within the vitrinite (huminite) macera1 group.     

STRUCTURAL GROUP ANALYSIS OF PRODUCTS FROM TWO-STAGE LIQUEFACTION OF HIGHVALE COAL

Products from liquefaction of Highvale Coal (Alberta. subbituminous) in anthracene oil and recycled product, with iron oxide catalyst, were studied using a structural group analysis method. The various functional groups were determined using a combination of proton NMR. carbon-13 NMR. IR. elemental analysis and nitrogen titration analysis. The liquefaction reactions in anthracene oil and in recycled product oil were compared on the basis of three solvent quality Indices and the predominant structural groups in the resulting liquids. The results show that major structural changes occur at both stages of liquefaction. Processing in anthracene oil showed much greater structural changes than liquefaction in the recycled product. The structural profiles Indicated a reduction in aromatic structures and a dramatic increase in aliphatic and naphthenic structures during processing in anthracene oil. These changes were attributed to the hydrogenation of aromatic structures and the dissolution of aliphatic and naphthenic compounds. Liquefaction in recycled product showed less significant changes in structural composition but resulted in a better quality product in terms of the amount of distillable oils, transferable protons and hydrogen to carbon ratio. This improvement was attributed to the improved availability of donatable hydrogen in the recycled product.     

三维射线追踪正演模型

本文叙述了利用射线追踪法生成多层曲界面三维正演模型的方法和原理。根据上述原理,在PDP11/45计算机上进行了试算,给出了三个模型实例,并对其在时间剖面上的三维地震响应进行了分析。     

粘土矿物的热模拟研究

本文介绍了粘土矿物的3个热模拟实验方法与结果;有常压下不同加热温度的实验;不同加热时间的实验;高压碱性介质下不同加热温度实验。讨论了粘土矿物受温度的影响、受热持续时间的影响、粘土脱水与烃类运移的关系及粘土矿物在高温高压下的变化。认为温度和持续时间是粘土矿物成岩转变的互相补偿的重要条件,压力是次要因素。蒙脱石向伊利石转化有利于孔隙度和渗透率的增大。