高温下煤焦的碳微晶及孔结构的演变行为

以贵州煤为原料,在热解温度950℃~1400℃制备了各种慢速和快速热解焦,主要对高温热解过程中煤焦的碳微晶和孔结构的演变行为进行了研究,同时也研究了高温气化过程中煤焦的孔结构变化规律。结果表明,慢速热解焦和快速热解焦的C和H含量明显不同;随热解温度的升高,煤焦的碳微晶结构向有序化方向发展,但慢速热解煤焦比快速热解煤焦的"石墨化"程度大;快速热解煤焦的微孔比表面积和微孔容积明显高于慢速热解煤焦,即快速热解煤焦的孔隙结构明显比慢速热解煤焦发达;在气化反应初期,煤焦的微孔比表面积下降,微中孔比表面积增加,反应后期煤焦的总比表面积快速下降。     

不同速率热解焦低温氧化增重现象及反应动力学

利用固定床热解反应装置和美国CDS-2500快速热解仪对胜利褐煤裂解,制得不同速率热解焦。借助热重分析技术,采用Achar微分法计算热解焦低温氧化增重特性及反应活化能。实验结果表明,快速热解焦的氧化增重量高于慢速热解焦。一级化学反应动力学模型可以很好地描述胜利褐煤焦的氧化增重反应,快速热解焦的氧化活化能较慢速焦低,快速焦更易发生低温氧化反应。     

滴管炉内新疆后峡煤挥发分释放和形态变化

对新疆后峡煤和滴管炉内的快速热解焦的比表面积、平均孔径、粒径和表面结构进行了分析,研究快速热解过程中原煤的形态变化。将热解焦在热重分析仪上进行气化实验,研究形态变化对气化反应的影响。结果表明,随热解温度的升高,煤焦比表面积与平均孔径变化趋势不同;快速热解过程中煤颗粒除破碎外,还会发生膨胀及凝聚形态变化;不同热解碎片气化趋势不一样,1200℃热解温度下的热解焦气化稳定性最好。     

碱／碱土金属催化松木屑快速热解机制

研究碱／碱土金属（AAEM）对生物质的热解及其热解产物组成的影响规律,可为生物质热解特性研究和热解产物的高效利用提供重要的理论依据。本文以松木屑为原料,将原样进行酸洗,并对酸洗样分别用K、Ca、Na和Mg氯化盐溶液浸渍,在500℃和Ar气氛下对各样品进行快速热解,考察了4种金属离子对松木屑热解产物组成分布的影响规律;通过热重分析考察了各个样品的热解特性;通过对热解生物油的气相色谱／质谱（GC／MS）分析考察了快速热解的焦油成分。研究结果表明：AAEM对松木屑有明显的催化作用,AAEM的存在能够提高热解气体和固体的产率,降低热解焦油的产率;AAEM能够降低热解温度,使热解更加容易进行;快速热解的焦油成分主要有酚类、酮类、醛类、芳烃、醇类、脱水糖类、呋喃类以及酸类,AAEM显著影响焦油产物组成,特别是呋喃类和芳烃的含量会有所增加。本文为优化生物质的热解条件与提高热解生物油品质具有重要意义。     

基于裂解气质联用分析的生物质逐级热解研究

为探究生物质快速热解反应历程,利用裂解气质联用仪对生物质进行逐级热解实验,考察在不同温度区间热解液体产物组分的分布规律。实验结果表明,生物质的化学组成和热解温度区间对热解液体产物都有重要影响。桉木在25℃~400℃热解液体产物较少,主要是吡喃和芳香类化合物,其中5,6-二氢-4-羟基-吡喃-2-酮相对峰面积随温度升高而降低;在450℃~500℃热解液体产物种类和产量均较多,主要以酮类和芳香类化合物为主。玉米芯热解规律和桉木的相似,但在25℃~350℃主要以呋喃类化合物为主,主要热解液体产物是2,3-二氢-苯并呋喃和2-甲氧基-4-乙烯基苯酚,在400℃~450℃热解液体产物以酮类化合物为主。生物质主要化学组分在不同温度区间热解得到不同液体产物,对其进行选择性热解,能够有效实现生物质资源的综合利用。     

高碳转化率下热解神府煤焦CO2高温气化反应性

用热天平等温热重法研究了6种不同热解速率和热解终温的神府煤焦在反应温度1200℃～1400℃的CO2气化反应性。研究了高碳转化率下，反应温度、热解终温和热解速率对快速和慢速热解焦高温反应性的影响。结果表明，快速热解焦比慢速热解焦的反应性好；随气化温度的提高，煤焦反应性的总体趋势增强，反应温度1300℃～1400℃时，3种快速热解焦的反应速率出现重叠；碳转化率为90%～98%时，慢速和快速热解焦的平均表观活化能为59.64kJ/mol～105.92kJ/mol和34.47kJ/mol～40.87kJ/mol，且气化反应以扩散控制步骤为主。     

晋城无烟煤加压快速热解特性及其对气化反应的影响

利用自行设计的加压热重固定床反应器进行了晋城无烟煤加压快速热解特性的研究,并结合热天平半焦等温热失重分析,考察了热解温度、停留时间和热解压力等外部操作条件对煤焦快速热解半焦特性的影响。结果表明,随热解温度的提高、停留时间的延长和热解压力的增大,所得到的半焦产率降低,气化反应性减弱,活化能提高;高温产生较小的比表面积,而停留时间的延长和压力的提高产生较大的比表面积,比表面积与气化反应速率无明显的依存关系。水蒸气气化速率是CO2的四倍左右。     

吡啶型氮快速热解中HCN和NH3生成机理研究

考虑煤中吡啶六元环与其他杂环的结合形式,对四种典型的吡啶型氮杂环结构及其热解中间产物中各键的Mayer键级进行了计算。通过对比Mayer键级的大小判断热解时最易发生断裂的键,进而对吡啶型氮热解时氮的逸出机理进行了分析。计算结果表明,吡啶型氮热解产生的含氮污染物主要是HCN;由于吡啶环与其他环结合方式的不同,氮的逸出过程也有差异。利用高频炉快速热解装置对吡啶和吖啶两种模型化合物进行了快速热解实验以验证计算结果。结果表明,吡啶和吖啶热解时虽有少量NH₃生成,但含氮污染物仍以HCN为主,实验结果可为计算所得的结论提供一定支持。
     

利用固体超强酸催化热解纤维素制备左旋葡萄糖酮

提出了一种纤维素催化热解制备左旋葡萄糖酮（LGO）的方法。通过Py-GC/MS实验,研究了纯纤维素快速热解的产物分布,以及热解温度、热解时间对纤维素生成LGO的影响;将固体超强酸（SO₄²-/TiO₂和SO₄²-/ZrO₂）和纤维素按1∶1的质量比机械混合后进行快速热解,考察了固体超强酸的催化对热解产物的影响。结果表明,纯纤维素快速热解时,主要在低温和中温的过渡温度区域内,同时发生脱水和解聚反应形成LGO;在固体超强酸的催化作用下,明显促进了LGO的形成,相对质量分数最高达60%以上。     

纤维素与草酸的慢速和快速共热解反应特性研究

本研究利用热重-傅里叶变换红外光谱和卧式固定床热解反应装置，探究了纤维素与草酸的慢速和快速共热解反应特性。慢速共热解的失重曲线包括草酸分解和纤维素分解两个阶段，由于草酸与纤维素分解不同步，草酸主要通过其分解形成的挥发分影响纤维素的分解，且影响并不明显。而在快速共热解中，草酸与纤维素同步热解，原料及挥发分之间有着充分的交互反应，因此，草酸对纤维素的三相热解产物具有显著影响。相比于纤维素单独快速热解，快速共热解形成的生物油中左旋葡聚糖、左旋葡萄糖酮含量减少，1,4∶3,6-二脱水-α-D-吡喃葡萄糖含量显著提高；热解气中CO减少，CO₂增多；此外，纤维素分解更为彻底，热解炭具有更高的芳香化程度。     

油藏化学工程研究的发展趋势

油藏化学工程是以三次采油为背景,在油藏工程和化学等相关学科的交叉领域中发展起来的,它主要是研究油藏环境中发生的传递现象和化学反应,及其影响油藏动态的原理与规律的学科。化学工程中一系列的新方法、新概念、新的理论原理的应用对油藏化学工程学科的形成将起到重要的推动作用,同时化学工程的发展与我国独特的自然资源和社会经济背景相结合将使其具有更强大的生命力。油藏化学工程研究的复杂环境和丰富的学科营养,为发展化学工程的前沿领域提供了广阔的园地。 为了更好地推进我国油藏化学工程研究的发展,文中提出了还需要加强的有关工作。     

A study of the mixture of coal and residue of the vacuum distillation of crude oil by thermal analysis

Thermal analysis was used for investigating the effect of the addition of the residue obtained from crude oil vacuum distillation on the carbonization process of brown coal. The kinetic analysis of the experimental TG curves was carried out by using the Coats-Redfern equation and then to select the most likely mechanism (functiong (α)) for particular decomposition stages of brown coal and its mixture with the residue. In the brown coal carbonization process the nucleation of a new solid phase is predominant. In the temperature range of the decomposition of coal (620–820 K) the addition of residue results a change in the mechanism of the thermal decomposition process — in the mixture three-dimensional diffusion processes and one-dimensional diffusion occur, depending on the composition. Above 730 K (secondary carbonation processes) the most likely mechanism involves the nucleation of a new solid phase as well as diffusion processes.     

Reduction of Recycled Barium Sulfate

Barium sulfate, which is recycled according to a new flowsheet of sodium sulfide production, was reduced by various carbon-containing materials (oil and furnace coke and Zh-grade coal). The reduction process was studied in comparison with the reduction of natural barite concentrate.     

Production of Oil by Hydrogenation of Coal

A survey of coal hydrogenation processes revealed that, despite a wealth of experience gathered in Germany up to 1945 some of which served as a basis for further work in the USA, there is at present no process available anywhere in the world for the commercial production of oil from coal. Approaches suitable for further development are the noncatalytic one-step limited hydrogenation and catalytic hydrogenation. Under the most favorable conditions production of oil from coal should become technically feasible some time between the early and mid-1980's. In view of the price of heavy fuel oil the commercial prerequisites for production of synthetic fuel oil from coal are presumably fulfilled only in those countries with low coal prices.     

Produced water treatment by nanofiltration and reverse osmosis membranes

Produced water, water that is co-produced during oil and gas manufacturing, represents the largest source of oily wastewaters. Given high oil and gas prices, oil and gas production from non-conventional sources such as tar sands, oil shale and coal bed methane will continue to expand resulting in large quantities of impaired produced water. Treatment of this produced water could improve the economic viability of these oil and gas fields and lead to a new source of water for beneficial use.Two nanofiltration and one low-pressure reverse osmosis membrane have been tested using three produced waters from Colorado, USA. The membranes were analyzed before and after produced water filtration using field emission scanning electron microscopy (FESEM), attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). In addition, membrane–water contact angles have been measured. XPS data indicate adsorption of organic and inorganic species during filtration. FESEM and ATR-FTIR data support theses findings. Water contact angles indicate the effect of membrane hydrophilicity on fouling. Our results highlight the value of using multiple surface characterization methods with different depths of penetration in order to determine membrane fouling. Depending on the quality of the produced water and the water quality requirements for the beneficial uses being considered, nanofiltration may be a viable process for produced water treatment.     

两种烟煤的液化及液化油的组成特征研究

在400℃、30min,7MPa冷氢压条件下两种煤液化结构表明,兖州煤比DECS－6（美国煤）煤更容易液化或共液化,这可能与兖州煤硫含量比较高有关,但DECS－6煤的油收率要高于兖州煤,表明EDCS－6煤容易裂解生成小分子化合物,同时种煤液化油的沸点分布特征基本一致。UV（紫外光谱）特征表明,液化油中单环芳烃主要为烷基取代苯类化合物,二环芳烃组分主要是烷基取代萘类化合物,三环芳烃主要为涉位缩合的菲类化合物,四环芳烃主要为芘、化合物,五环芳烃以苯并芘类化合物为主,而极性化合物可归属为含O、S、N的极性芳香化合物。     

Inevitable revival of C1 chemistry in the first half of the twenty-first century

The future of fuel production via C₁ chemistry is discussed in this paper. Four different processes from coal or natural gas to methanol or gasoline are compared with the present commercialized process from crude oil to gasoline on the aspects of economics, environmental friendliness and energy. Considering the future trend of crude oil price, it is believed that C₁ chemical technologies, especially indirect conversion technologies, will become economically feasible by the year 2030.     

The Future of Gas to Liquids as a Gas Monetisation Option

The paper introduces gas to liquids (GTL) as a monetising option from a technology, marketingand project perspective. GTL is complementary to LNG and pipelines. At the same time, using naturalgas as a source for fuels in the form of GTL helps countries around the world to diversify their energysupplies. Furthermore, gas-based products are inherently cleaner than oil products. Shell‘s proprietary GTL technology or SMDS (Shell Middle Distillates Synthesis), is discussed in some detail. The paperalso covers the challenges for successful implementation of GTL projects and why Shell is well positionedto take a lead in the industry on the basis of its long standing and broad experience in GTL research,plant operations, marketing and excellent track record in mega projects in the last thirty years. Shell‘scommitment to GTL is best demonstrated by the recent signing of a Heads of Agreement with Qatar Petroleum for the construction of the world‘s largest GTL plant. A key success factor is Shell‘s experiencewith marketing quantities of high quality GTL products from its 12,500 barrels per day plant at Bintulu,Malaysia since 1993. Further marketing opportunities will arise when new GTL capacity comes on-streamin the middle east when more quantities will become available to bulk users. Amongst the most interesting market will be automotive transportation, where clean GTL fuels can be positioned as an ‘alternativefuel beyond oil‘ providing energy security to host countries. Shell is actively engaging with a numberof regulators, automotive companies and governments worldwide including China, to demonstrate theperformance of GTL and its cost effectiveness in reducing local emissions. An added benefit is that GTLcan use existing infrastructure and requires no investment. Finally, the paper briefly discusses the coal toliquids (CTL) process as an alternative route to produce high quality GTL products and the key issuesrelating to the process.     

神府煤Ni-Mo-S/Al_2O_3催化液化动力学研究

对煤液化产物进行溶剂的分级处理,采用集总的方法得到Ni-Mo-S/Al2O3催化神府煤液化动力学模型。该模型包括了煤、前沥青烯、沥青烯和油气之间的相互转化,考虑了连串反应、平行反应和逆向转化以及结焦反应的影响,可以较好地模拟Ni-Mo-S/Al2O3催化神府煤液化过程。基于建立的Ni-Mo-S/Al2O3催化神府煤的动力学模型,求得神府煤催化液化的表观活化能为125~244 kJ/mol。通过对计算得到的模型参数分析表明,在高温阶段存在明显的油气向沥青烯以及沥青烯向前沥青烯的逆向转化。当温度高于420℃时,出现前沥青烯和沥青烯结焦反应现象。     

马家塔煤及其显微组分的加氢液化特征

用Fe2O3作催化剂,硫黄为助催化剂,脱晶蒽油为循环溶剂,在反应温度为450度,初始氢压为10MPa,反应时间为60min的实验条件下,在微型高压釜内对马家塔原料煤及其显微组分的加氢液化特征进行了系统研究,镜质组的液化反应性高于惰质组,在原料煤,镜质组和惰质组这三种实验原料中,原料煤的液化反应性是最高的,对总转化率和油收率而言,原料煤＞镜质组＞惰质组,对沥青烯产率而言,原料煤＞惰质组＞镜质组,水产率则是镜质组＞原料煤＞惰质组,气产率为惰质组＞镜质组＞原料煤,原料煤,镜质组和惰质组在加氢液化过程中所产生的气体在组成上也是有所差异的,各显微组分在加氢液化过程中可能存在着协同作用。