Co-pyrolysis characteristics and interaction route between low-rank coals and Shenhua coal direct liquefaction residue

To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.

Mechanisms and characteristics of mesocarbon microbeads prepared by co-carbonization of coal tar pitch and direct coal liquefaction residue

DCLR-P was prepared by direct coal liquefaction residue (DCLR) with ash removal.In the present experiments,mesocarbon microbeads (MCMBs) were prepared by co-carbonization of coal tar pitch (CTP) and DCLR-P.With the increase of DCLR-P content,the yield of MCMBs increased from 47.8% to 56.8%.At the same time,the particle sizes distribution of MCMBs was narrowed,resulting in the decrease of D9o/D10 ratio from 154.88 to 6.53.The results showed that DCLR-P had a positive effect on the preparation of MCMBs.1H-NMR,FTIR,SEM and XRD were used to analyze the mechanisms and characteristics of MCMBs prepared by co-carbonization of CTP and DCLR-P.The results showed that the Proton Donor Quality Index (PDQI) of DCLR-P was 13.32,significantly higher than that of CTP (0.83).This indicated that DCLR-P had more naphthenic structure than CTP,which leads to hydrogen transferring in polycondensation reaction.The aliphatic structure of DCLR-P can improve the solubility and fusibility of mesophase,thereby making the structure of MCMBs more structured.The microstructure of the graphitized MCMBs had a substantially parallel carbon layer useful for its electrical performance.The performance of graphitized MCMBs as a negative electrode material for Li-ion batteries was tested.The particle sizes,tap density,specific surface area and initial charge-discharge efficiency of graphitized MCMBs met the requirements of CMB-I in GB/T-24533-2009.However,the initial discharge capacity of graphitized MCMB was only 296.3 mA h g-1 due to the low degree of graphitization of MCMBs.

Compatibility Evaluation between Direct Coal Liquefaction Residue and Bitumen

The compatibility between direct coal liquefaction residue(DCLR) and five kinds of pure bitumen(Shell-90,SK-90, ZSY-70, DM-70 and KLMY-50) was evaluated in this study. The rheological characteristics, glass transition temperatures(T_g), solubility parameters(SP) and SARA(saturates, aromatics, resins, and asphaltenes) fractions of DCLR,five kinds of pure bitumen and their blends(named as DCLR modified bitumen) were measured using the dynamic shear rheometer(DSR), differential scanning calorimetry(DSC), viscosity, and SARA tests, respectively. And the compatibility between DCLR and pure bitumen was characterized with three approaches, viz. the Cole-Cole plot,T_g, and the solubility parameter difference(SPD) method. Since each method has its own working mechanism, the compatibility ranking for the DCLR and five kinds of pure bitumen is slightly different according to the three approaches. However, the difference is pretty close and sometimes can be ignored. The general compatibility ranking decreases in the following order: Shell-90≈SK-90>DM-70≈ZSY-70>KLMY-50, which is affected by the asphaltenes content and the colloid index(I_c) value in the pure bitumen. Pure bitumen with lower asphaltenes content and colloid index(I_c) value has better compatibility with DCLR.

Discharge characteristics of coal and extraction residue from direct coal liquefaction in partial fluidization silo

Gasification of extraction residue(ER) from direct coal liquefaction with pulverized coal is an efficient way for the utilization of carbonaceous wastes, which improve the overall efficiency of direct coal liquefaction technology. The discharge characteristics of ER mixing with pulverized coal is important paraments for its gasification process, which is seldom studied in the literature. In this study, the discharge characteristics of the pulverized coal(M1) as well as its mixture with ER(M2) were systematically investigated in an atmospheric pressure partial fluidization silo with different fluidization apparent velocity. It was observed that although M2 is a viscous powder with lower flowability than M1, the mass flow rate of M2 is 65% higher than M1 at the 3.7 mm·s-1apparent gas velocity. M2 exhibits the properties of Geldart A type powder, which improves the mass flow rate and stability of the discharged material. The mass flow rate of both M1 and M2 first increases and then slowly decreases with the increase of apparent gas velocity of the fluidizing air, which means the discharge process of M1 and M2 can be optimized by the apparent gas velocity.

基于正交设计和灰色关联理论的DCLR改性沥青优化与机理研究

基于不同工艺条件下煤直接液化残渣(direct coal liquefaction residue,DCLR)改性石油沥青,通过设计三因素三水平正交试验,得到DCLR改性沥青的最佳工艺条件为剪切搅拌时间45 min、剪切搅拌温度150℃、剪切搅拌速率4000 r/min;通过灰关联度分析,发现针入度、软化点、延度、PI这4个指标的影响权重不一,主次顺序分别为针入度>PI>延度>软化点.利用BP神经网络对改性沥青的性能(针入度)进行模拟和预测,预测值与实验数据拟合度为0.993,证明了该方法的有效性.采用红外光谱、热重和扫描电镜对改性沥青进行分析.结果表明:DCLR与沥青之间没有发生明显的化学变化.在确定其最优配比的基础上,通过车辙试验、小梁弯曲试验、冻融劈裂试验来评价混合料的高温性能、低温性能和水稳定性能,结果表明:DCLR能明显改善沥青的高温性能和水稳定性,但对其低温性能影响不大.

Study on the corrosion of refractory materials by coal blended with the extraction residue of direct coal liquefaction in a simulated gasification atmosphere

Utilizing the extraction residue(ER)of direct coal liquefaction residue as a gasification feedstock has significant economic value.But the characteristic of high ash and iron in the ER would increase the risk of corrosion of the refractory materials and affect the long-term operation of the gasifier.In this work,corrosion experiments of molten slag derived from a mixture of 20 wt%ER and 80 wt%coal on a high-chromia refractory brick and SiC brick were carried out using a rotary-drum furnace in a simulated gasification atmosphere.The experimental results show that the viscosity of the poured slag is larger as compared to the initial ash sample at the same temperature,which suggests that the viscosity-temperature relationship of the poured slag should be used as the reference for the operation temperature of the gasifier to ensure that the slag can flow during operation.For a high-chromia refractory brick,iron oxides in molten slag could react with Cr_(2)O_(3) in the refractory matrix but,because the aggregate was not found to be damaged,the damage to the matrix structure was the key factor for causing the corrosion of the high-chromia refractory brick.Metallic iron was observed in the exposed SiC brick,which indicated that the reaction between the iron oxides in the slag and SiC occurred,forming metallic iron and SiO_(2).The corrosion of a SiC brick by molten slag depended mainly on the dissolution of Al_(2)O_(3) particles and the reaction between iron oxides in the molten slag and SiC particles.Therefore,the high iron content in coal ash had a serious influence on the corrosion of refractory materials.More efforts need to be made on coal blended with ER as a gasification feedstock in the future.

煤液化固渣萃余物的组成结构及铁催化剂活性相回收

为解决大规模煤直接液化催化剂铁源供应问题,同时实现煤液化固渣萃余物的无害化分质利用,从固渣萃余物中回收铁催化剂的角度进行研究,探索采用物理磁选法进行铁催化剂富集回收的可行性。首先采用粒度分析、XRF、XRD、SEM、TG、SEM-EDX等表征手段对固渣萃余物进行全面的物化性质表征,确定铁催化剂的质量分数和存在形态。由分析可知,工业装置固渣萃余物主要由未反应煤中的炭及残炭、挥发分及灰分组成,其粒度均匀且没有团聚,其中铁元素质量分数为5.96%,铁物种仍以具有顺磁性的Fe1-xS活性相存在,被未反应煤、残余沥青掺杂、包裹,与各种元素Ca、Si、Al、O等均匀混杂分布在萃余物中。在此基础上,选用4种型式的磁选设备在不同磁场强度下进行磁选富集,并将富集后的样品作为催化剂用于煤直接液化反应,考察其直接液化反应性能。试验结果表明,湿式立环脉动高梯度磁选机一方面将所产生的高梯度磁场力作用于磁性催化剂细粉,同时脉动流体力在一定程度上消除了非磁性颗粒的机械夹杂。在清水作为分散介质及洗涤介质下,更有效地实现了固渣萃余物中铁催化剂细粉的精细分离。在640000 A/m外加磁场强度下,含铁催化剂物料富集率为10.48%,铁元素质量分数可达11.37%,高压釜萃取油产率为41.96%,与无催化剂时相比高7.17%,比固渣萃余物提高8.99%,可掺混至新鲜催化剂中实现有效回用,部分解决催化剂铁源短缺的问题。

基于正交设计的复合DCLR改性沥青制备及性能研究

为解决DCLR改性沥青相容性较差,导致沥青离析指标不合格的问题,采用改性剂LOK、催化裂化油浆FCC、多聚磷酸PPA对DCLR改性沥青进行复合改性,加入后改性沥青基本无离析现象。通过三因素三水平正交试验,对Box-Behnken效应面法作进一步优化。以10℃延度为主要评价指标,软化点、针入度为次要评价指标得出最佳掺量。采用荧光显微镜观察样品荧光图谱,借助DSR、BBR等流变学仪器对样品以及SBS改性沥青进行对比分析,研究其高低温性能。结果表明:当掺量配方为9.5%DCLR+6.6%FCC+0.97%LOK+0.49%PPA(质量分数)时,复合改性沥青性能最佳,且储存稳定性优异;高温性能优于SBS改性沥青,低温性能与SBS改性沥青差异较小,路用性能优异。

煤直接液化油渣萃余物组成、性质分析及应用场景探讨

煤直接液化油渣用洗油萃取后再经离心分离、常减压闪蒸等工艺处理,分离沥青质后可得到不同等级的沥青产品以及萃余物,将萃余物大规模利用,可以大大提高企业的经济效益。分析了萃余物的族组成、性质,在此基础上讨论了萃余物应用于配煤气化、循环流化床锅炉掺烧、炭灰分离的可行性。分析认为:萃余物更适合通过配入原料煤应用于干粉煤气化。

DCLR改性沥青宏观性能与微观相对分子质量分布关系

为了研究煤直接液化残渣（direct coal liquefaction residue,DCLR）改性沥青宏观性能与微观相对分子质量分布的关系,以70#沥青为基质沥青,对DCLR掺量（DCLR与基质沥青的质量比）分别为5%,10%,15%和20%的改性沥青,利用PG分级体系和针入度分级体系分析了DCLR对沥青宏观性能（高温性能、低温性能、疲劳性能）的影响;同时,采用凝胶色谱仪测试DCLR改性沥青的相对分子质量分布,分析分布参数LMS（大分子区）,MMS（中分子区）和SMS（小分子区）所占比例与沥青宏观性能之间的关系.结果表明：DCLR可显著改善沥青的高温性能,但也会明显降低沥青的低温性能和疲劳性能;DCLR改性沥青更适合作为沥青路面结构的中面层来提高路面的高温抗变形能力,建议DCLR的掺量为5%,适用于1～4气候分区;相对分子质量分布参数LMS所占比例与沥青的宏观性能具有显著的相关性,据此可建立两者在不同温度下的指数关系模型.

神华煤直接液化残渣理化特性与分子结构特征研究

煤液化残渣制备高端炭材料是目前煤直接液化技术领域研究的热点,该过程实现的关键在于煤液化残渣的深度脱灰,而深度脱灰工艺技术开发需要对液化残渣理化特性与分子结构有深入的认识。以神华煤液化残渣为研究对象,借助TG-DTG探究了液化残渣的失重特性;借助激光粒度仪和透射电镜(TEM)分别研究了液化残渣在洗油和四氢呋喃两种溶剂中的粒度分布特性和颗粒形貌特征;在正负离子(±ESI)和正离子大气压光电离(+APPI)模式下,利用傅里叶变换离子回旋共振质谱仪(FT-ICR MS)对液化残渣的分子结构组成进行了鉴别。研究结果表明:液化残渣的主要失重温区为300℃~600℃,466℃时失重速率最大,此时的活性最高;液化残渣在洗油或四氢呋喃中的粒度呈现百纳米级正态分布,残渣在洗油中粒度分布更为集中且粒径更小;液化残渣中含丰富的N1、N2类含氮杂环以及O1、O2、O3、CH类含氧多环的芳香分子构型。

ZnO对DCLR改性沥青抗永久变形及抗紫外老化性能影响

为了探究氧化锌(ZnO)对煤直接液化残渣(DCLR)改性沥青的抗永久变形及抗紫外线老化性能的影响规律,制备了不同ZnO掺量DCLR改性沥青,分别进行了多重应力蠕变恢复试验(MSCR)和全断面断裂能量试验。试验结果显示:当ZnO掺入DCLR改性沥青后,随着ZnO掺量的逐渐增大,DCLR改性沥青的Jnr逐渐减小、R逐渐增大、温度升高时的Jnr增幅与R降幅均减小、DCLR改性沥青断裂能密度增大且因随紫外老化时间的延长而造成的降速变慢,表明ZnO能够降低DCLR改性沥青温度敏感性、提高DCLR改性沥青抵抗永久变形能力及抗紫外线老化性能。

DCLR Modifi ed Petroleum Asphalt Optimization and Mixture Road Performance

In recent decades,modified asphalt materials have been used in enhancing the traffic load on the roads.The main objective of this paper is to explore the modifi cation effect of direct coal liquefaction residue(DCLR)on as-phalt binders and investigate the effectiveness of DCLR in improving the performance of asphalt road.This paper prepared modifi ed petroleum as-phalt under diff erent process conditions and tested its penetration,softening point and ductility index.Based on the experimental data,according to gray correlation degree,the performance for the asphalt was compared.The performance for the modified asphalt is simulated and predicted using poly-nomial functions.The modifi ed asphalt was analyzed by FT-IR,TGA,SEM and HPLC.The results show that the optimal process conditions for DCLR modifi ed asphalt are shear mixing time of 45 min,shear mixing tempera-ture of 150℃ and shear mixing rate of 4000 r/min.The predicted fit with the experimental data of 0.993 further demonstrates the effectiveness of the method.The characterization results show no significant chemical change between the DCLR and the asphalt.DCLR can significantly improve the high temperature performance and water stability of the asphalt,but it has little impact on its low temperature performance.

富钠液化残渣CO_(2)气化过程煤焦结构演化及钠赋存形态迁移规律

本研究采用N2吸附-脱附、FT-IR、XRD、SEM和Raman分析,考察了富钠液化残渣CO_(2)气化过程煤焦结构演化和钠赋存形态变迁规律。实验结果表明,富钠液化残渣钠离子高温下易诱导液化残渣孔结构发生变化,拓展了介孔结构,介孔体积由0.05 cm^(3)/g增加至最大0.16 cm^(3)/g。随气化反应进行,煤焦中相继出现不同晶体化合物,XRD分析显示多数晶体矿物质为含钙矿物质,没有明显含钠矿物质的衍射峰,是钠离子高温下易挥发及含钠化合物晶体存在缺陷所致。与含钠矿物质相比,含钙矿物质更易与液化残渣中铝硅酸盐反应,从而使含钠矿物质气化过程保持了催化活性。煤焦(GR+VL+VR)/D的比率先升高后降低,分别与芳香族的解离及小芳香环结构重排成大芳香环结构有关。此外,钠离子释放率与气化反应时间密切相关,液化残渣中大部分钠离子在气化初期挥发至气相,与负载水溶性钠盐液化残渣相比,富钠液化残渣钠离子高温释放率较低。

煤液化残渣萃余物与煤共气化的灰渣特性

与煤共气化是实现煤直接液化残渣萃余物(ER)资源化利用,提升煤直接液化工程整体经济性的重要途径。气化过程灰渣的流动性是影响气化操作条件的重要参数,利用灰熔点仪、高温旋转黏度计、XRD及SEM等测试手段考察了ER与煤共气化的灰渣熔融特性、黏温特性及晶体特性,并结合壳牌气化装置入炉煤配比和操作条件,从灰化学角度确定ER的最佳掺混比例及气化操作窗口。结果表明:ER属于高灰、高铁、高钙、高硫物质,且其灰成分偏碱性,随煤中ER添加量增大,掺混后的灰分、铁含量和硅铝比逐渐增大。当萃余物质量分数超8%,全液相温度T_(liq)降低,但萃余物添加量超20%时,熔渣类型从玻璃渣转变为结晶渣。XRD与SEM分析结果表明钙长石的析出造成熔渣类型改变,钙长石的析出主要是因为萃余物的添加使熔渣黏度降低,熔渣中团簇的扩散能力增强,有利于结晶行为。结合Shell气化炉的操作条件及对煤灰中铁含量的要求,当萃余物添加量为10%时,共气化熔渣适合气化炉排渣,对应的排渣窗口为1 335~1 557℃。该研究结果为ER与煤共气化提供指导,提高煤直接液化流程的经济性。

液化残渣气化过程钠/铁协同催化作用及对焦结构演化的影响规律

高钠煤直接液化后碱金属钠富集于液化残渣中,相比原煤,残渣的钠含量升高4~10倍,利用残渣固有钠及残留的铁基液化催化剂对液化残渣进行催化气化提质,是其资源化高效利用的理想方案。通过煤直接液化实验制取了钠含量较高的高碱液化残渣,研究了高碱液化残渣在气化过程中钠/铁协同催化的反应性,并建立适宜的动力学模型,考察了协同催化反应的动力学过程。围绕钠/铁间高温相互作用规律,通过联合FTIR,XRD,ICP-AES等技术,详细分析了气化焦有机结构、矿物质组成及钠高温释放率等。结果表明:钠/铁协同催化过程的活化能为66 kJ/mol~69 kJ/mol,与高碱液化残渣单独气化相比均有所降低,残渣最高气化反应性指数超过0.45°/min,相同温度下液化残渣最大反应速率分别增大了1.17倍(900℃)、1.33倍(1000℃)和1.14倍(1100℃);双金属间表现出明显的协同催化效应,n(Na)/n(Fe)对液化残渣气化反应性有一定影响,铁含量较高时易形成弱催化活性的铁/碱金属化合物K-Fe,Na-Fe和Li-Fe等,从而降低协同催化活性,且气化温度升高有利于强化铁与碱金属间结合作用;XRD分析同样证实,适量的铁基催化剂能够阻止钠与Si,Al反应生成无催化活性的矿物质,更好维持钠催化活性;钠/铁除具有协同催化效应外,含铁矿物对气化过程钠的高温释放过程还有显著抑制作用,相比高碱液化残渣单独气化,添加铁基催化剂后钠挥发量减少了9.6%~26.7%。

煤直接液化残渣资源化利用研究进展

煤直接液化残渣是直接液化工艺副产物,产量约占原煤质量的10%~30%。液化残渣组成成分复杂、环境危害大且处理成本高,同时其含有重质油和沥青烯等物质,有潜在的二次利用价值,因而资源化利用煤直接液化残渣,间接提高煤有机质原子利用率并降低工艺经济成本,成为当前煤直接液化工艺亟待解决的关键技术问题。综述了煤直接液化技术及液化残渣资源化利用的最新研究进展,深入探讨了不同影响液化残渣高效转化的关键因素,分析比较了不同液化残渣处理工艺技术的特点,以期为煤直接液化技术发展及液化残渣资源化利用提供指导。

碱激发煤液化残渣基地聚物的力学及微观特性

以煤液化残渣(DCLR)为原材料制备了煤液化残渣基地聚物(DG),并通过调节碱激发剂(AA)模数及其掺量、养护龄期及DCLR粒径,研究了DG试样的工作性能、力学性能、微观结构及化学组分变化.结果表明:DG的无侧限抗压强度与抗折强度均随着AA模数与掺量的增加呈先增加后降低的趋势,在AA模数为1.4、掺量为50%时,试样中硅铝酸盐凝胶最多,结构最致密,强度最大;DG试样的早期强度较高,其1 d抗压强度与抗折强度均达到28 d的70%以上;AA模数的改变对DG浆体流动度的影响并不显著;DCLR粒径越小,DG试样的力学性能越好,且DCLR粒径越大,DG试样养护7 d后强度提升越快.

煤液化残渣流化床热解工艺研究与碳减排分析

本文首先对煤液化残渣的原料进行了分析,并使用固定流化床反应器进行了实验研究。在实验结果的基础上,利用Aspen Plus软件对流化床热解过程进行了模拟,并对不同工艺过程的物料平衡和能量平衡进行了分析。通过对比不同工艺设计案例的能源效率、碳效率、固体废物排放量、CO_(2)排放量等指标,最终提出了一种灵活流化热解(FFP)耦合太阳能水电解的方法,将绿色氢气和绿色氧气引入该工艺,可以实现原料中碳、氢元素近乎完全利用,并生产出高品质的液体燃料和化学品,这一新工艺可以在整个工艺中实现近乎零碳排放。由于使用绿色氧气作为助燃剂,所产生的焦炭中的所有碳都可以转化为合成气并用作下游化工生产的原料气。因此,当一个70万t·a^(-1)的煤液化残渣流化床热解装置耦合电解水装置,该工艺的总碳效率可达到99.52%,是所有工艺中碳效率最高的,CO_(2)排放量从83737.67Nm^(3)·h^(-1)降至3739.75Nm^(3)·h^(-1)。该技术原理可以推广应用于有机固废热解、催化裂化、流化焦化等传统烧焦供热的工艺过程的碳减排过程优化。

煤液化残渣综合利用研究进展

我国拥有丰富的煤炭资源,但石油资源相对贫乏,对外依赖度高,因此发挥我国煤炭能源优势,大力发展煤直接液化技术就成为改善我国能源结构的重要选项之一。煤液化残渣是煤炭直接液化后的主要副产品,约占液化原料的20%~30%,是一种极具利用价值的重质碳资源。当前,煤液化残渣的利用方式有气化、热解、焦化、碳材料和沥青改性剂等,但由于组成复杂,从而限制了其所含组分的高效利用,因此本文对如何合理高效利用煤液化残渣组分的当下研究热点展开论述。