A density functional theory study on the decomposition of aliphatic hydrocarbons and cycloalkanes during coal pyrolysis in hydrogen plasma

To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.

Thermodynamical Study on Production of Acetylene from Coal Pyrolysis in Hydrogen Plasma

The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show that the hydrogen concentration in the equilibrium system is very important for the acetylene production by coal conversion and the energy consumption for the production of acetylene per-kilogram strongly depends on the hydrogen concentration and the temperature.

CFD Simulation of a Hydrogen/Argon Plasma Jet Reactor for Coal Pyrolysis

A Computational Fluid Dynamics(CFD) model was formulated for DC arc hydrogen/argon plasma jet reactors used in the process of the thermal H_2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete data, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-εequations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.

Characterization of Carbon Deposits Formed During Plasma Pyrolysis of Xinjiang Candle Coal

Carbon deposits were formed on the reactor wall during plasma pyrolysis of the Xinjiang candle coal in our V-style plasma pyrolysis pilot-plant. The carbon deposits were studied using a scanning electronic microscope （SEM） and the X-ray diffraction （XRD） method. It was found that carbon deposits located at different parts in the reactor exhibited different microscopic patterns. The formation mechanism of the carbon deposits was deduced. The downward increase in the graphitization degree of the carbon deposits was found and interpreted.

Influence of dispersants on coal-water slurry prepared from the solid residue of plasma pyrolysis of coal

This work presents the influence of dispersants on coal-water slurry(CWS),which was prepared from the solid residue of plasma pyrolysis of coal.The effects of dispersant type,solid concentration,dispersant content,and temperature on the rheological properties of CWS are examined.A suitable empirical model regarding the relation between viscosity and temperature is proposed.Through the sedimentation experiment of CWS,dispersants are found to significantly promote the stability of CWS.

Isolated 4-20 mA Current-Loop System in the Experiment of Coal Pyrolysis in H-plasma Producing Acetylene

The purpose of this paper is to demonstrate a systematic approach to design high performance signal conditioning circuits,and to show how to implement the 4-20 mA analog current-loop transmitter and receiver circuits by using isolation amplifier.The basic principle and typical applicable circuits of the 4-20 mA current loop isolation chip T1100N,the current-limiting circuit and filter circuit are presented.And the experimental testing data of the circuits are analyzed.

Physicochemical,mineralogy,and thermo-kinetic characterisation of newly discovered Nigerian coals under pyrolysis and combustion conditions

In this study,the physicochemical,microstructural,mineralogical,thermal,and kinetic properties of three newly discovered coals from Akunza(AKZ),Ome(OME),and Shiga(SHG)in Nigeria were examined for potential energy recovery.Physicochemical analysis revealed high combustible but low levels of polluting elements.The higher heating values ranged from 18.65 MJ/kg(AKZ)to 26.59 MJ/kg(SHG).Microstructure and mineralogical analyses revealed particles with a rough texture,surface,and glassy lustre,which could be ascribed to metals,quartz,and kaolinite minerals.The major elements(C,O,Si,and Al),along with minor elements(Ca,Cu,Fe,K,Mg,S,and Ti)detected are associated with clays,salts,or the porphyrin constituents of coal.Thermal analysis showed mass loss(ML)ranges from 30.51%to 87.57%and residual mass(RM)from 12.44%to 69.49%under combustion(oxidative)and pyrolysis(non-oxidative)TGA conditions due to thermal degradation of organic matter and macerals(vitrinite,inertinite and liptinite).Kinetic analysis revealed the coals are highly reactive under the oxidative and non-oxidative conditions based on the Coats-Redfem Model.The activation energy(Ea)ranged from 23.81 to 89.56 kJ/mol,whereas the pre-exponential factor(kQ)was from 6.77×10^(-4)/min to 1.72×10^(3)/min under pyrolysis and combustion conditions.In conclusion,the coals are practical feedstocks for either energy recovery or industrial applications.

Thermal behavior of Mongolian low-rank coals during pyrolysis

Low temperature pyrolysis behavior of four low-rank coals from the biggest deposits of Mongolia were studied using a fixed-bed reactor and Gray-King retort.The coal samples and resultant chars were analyzed using Fourier transform infrared spectroscopy(FTIR),^(13)C nuclear magnetic resonance(^(13)C NMR)to explore the structure changes and thermogravimetric analyzer coupled with mass spectrometry(TG-MS)was used to investigate the pyrolysis reactivity of coal during thermal decomposition process.The results showed that the aliphatic structure in coal was significantly reduced and the carboxyl groups almost completely decomposed during pyrolysis process at 600℃.The tar yield of Gray-king test is higher than that obtained from the fixed-bed reactor.The gaseous evolution measured by TG-MS during pyrolysis showed that the maximum peaks of evolution of CH_(4),H_(2),C_(2)H_(2),C_(2)H_(5),CO,and CO_(2) gases were well corresponded to the maximum rate of weight loss in the range 428-445℃.

Synergistic reaction behavior of pyrolysis and reduction of briquette prepared by weakly caking coal and metallurgical dust

Co-carbonization of weakly caking coal and zinc-containing dust to prepare highly reactive ferro-coke and collaboratively recover zinc powder is one of the feasible ways for steel enterprises to recycle zinc-containing dust.The pyrolysis mass loss behavior of adding blast furnace dust with different zinc contents to different ferro-coke materials was systematically studied by thermogravimetry and differential thermogravimetry analysis,and the kinetic mechanism of pyrolysis-reduction reaction of hybrid briquette was explored.The results of thermogravimetric curve analysis show that the addition of zinc oxide to the sample has no significant effect on the mass loss rate of the sample below 580℃,and the pyrolysis mass loss of zinc oxide mainly occurs between 800 and 1000℃.Kinetic analysis results show that the pyrolysis of zinc-containing samples is controlled by chemical reactions below 580℃.The reaction at 580–700℃ is controlled by the nucleation and growth model,and that above 700℃ is mainly controlled by diffusion.The results of X-ray diffraction analysis show that the pyrolysis process can effectively remove zinc oxide from ferro-coke.

A Preliminary Study of the Plasma Pyrolysis of Waste Tyres

Thermal plasma pyrolysis of waste tyres for recovering energy was performed in a nitrogen plasma reactor. The main gaseous products were identified by chromatography as H2, CO, CH4, C2H2 and so on. From a series of experiments, the effects of the process parameters of thermal plasma pyrolysis were investigated. Under our experimental conditions with steam injection, the total contents of H2 and CO reached up to 38.3% in the gas product, C2H2 up to 4%, and the maximum calorific value of the pyrolysis gas was 8.96 MJ/m3. The results indicate that plasma-assisted thermal decomposition of waste tyre particles may be a useful way for recovering energy and useful chemicals.

不同气氛下富油煤受热裂隙演化及热解动力学参数变化

富油煤的清洁高效开发有助于保障我国的能源安全。选择柠条塔矿富油煤,开展了N2和欠氧气氛条件下的加热试验,利用体视显微镜获取不同温度处理后富油煤的表观形貌,在氩气气氛中,对富油煤在0~600℃下热重(TG)、微商热重(DTG)、差示扫描量热(DSC)进行测试,基于激光闪射法监测富油煤热导率变化,并分析了不同升温速率下活化能、频率因子等热解动力学参数的变化规律,探讨富油煤热处理后裂隙演化和热解动力学参数变化。研究结果表明:随着加热温度的升高,富油煤表面裂隙数目明显增多,逐渐贯通,且镜煤裂隙发育程度更高。相比N2气氛,同温度下欠氧气氛中煤样裂隙率更高。质量损失率变化趋势与裂隙率相似,由于欠氧环境中煤样发生氧化反应,导致其增速更快。N2气氛中富油煤质量损失率与裂隙率迅速提升的温度点明显滞后于欠氧气氛。室温至350℃范围内,由于热膨胀影响,富油煤热导率随着温度升高有所增加。根据热重分析,富油煤随温度变化可分为室温至300℃、300~500℃和500~600℃3个阶段,在阶段Ⅰ和Ⅱ分别由于吸附水析出和有机质的分解吸热,频率因子和活化能逐渐增大;在阶段Ⅲ由于无机矿物的分解放热,频率因子和活化能降低。研究结果有助于理解富油煤高温开发过程中的结构演化机制和传热机理。

Mechanisms of carbon isotopic fractionation in the process of natural gas generation: Geochemical evidence from thermal simulation experiment

Low maturity coal samples were taken from the Ordos Basin to conduct gold tube thermal simulation experiment in a closed system,and the characteristics of the products were analyzed to find out the fractionation mechanism of carbon isotopes and the causes of abnormal carbon isotopic compositions of natural gas.At the heating rates of 2℃/h(slow)and 20℃/h(rapid),the low maturity coal samples of the Ordos Basin had the maximum yields of alkane gas of 302.74 mL/g and 230.16 mL/g,theδ13C1 ranges of-34.8‰to-23.6‰and-35.5‰to-24.0‰;δ13C2 ranges of-28.0‰to-9.0‰and-28.9‰to-8.3‰;andδ13C3 ranges of-25.8‰to-14.7‰and-26.4‰to-13.2‰,respectively.Alkane gas in the thermal simulation products of rapid temperature rise process showed obvious partial reversal of carbon isotope series at 550℃,and at other temperatures showed positive carbon isotope series.In the two heating processes,theδ13C1 turned lighter first and then heavier,and the non-monotonic variation of theδ13C1 values is because the early CH4 is from different parent materials resulted from heterogeneity of organic matter or the carbon isotope fractionation formed by activation energy difference of early enriched 12CH4 and late enriched 13CH4.The reversal of carbon isotope values of heavy hydrocarbon gas can occur not only in high to over mature shale gas(oil-type gas),but also in coal-derived gas.Through thermal simulation experiment of toluene,it is confirmed that the carbon isotope value of heavy hydrocarbon gas can be reversed and inversed at high to over mature stage.The isotope fractionation effect caused by demethylation and methyl linkage of aromatic hydrocarbons may be an important reason for carbon isotope inversion and reversal of alkane gas at the high to over mature stage.

产物导向与机器学习驱动的富油煤热解提油热效应评估

煤炭热解过程的热效应是煤炭热解机理研究、反应器设计等过程的关键参数。目前关于煤炭热解热效应的评估方法之间精度差异较大,其中应用最多且可行性最大的方法为基于同步热分析仪(TG-DSC同步联用)来进行测定,但该方法依然对仪器的测量精度依赖较大,且在得到热流曲线之后的热效应计算方法之间精度也存在差异,导致数据的可重复性差,难以适应大规模生产及工艺设计的需要。富油煤含有较多的脂肪侧链、桥键等富氢结构,在热解过程中受热裂解生成更多的焦油,是良好的煤制油原材料。热解工艺的调控是影响富油煤热解所制焦油品质的关键因素,这其中热解过程的热效应又是热解工艺开发的重要参数,因此无论是对富油煤热解还是对广义的煤炭转化来说,都迫切需要开发准确、高效的煤炭热解热效应评估方法。基于富油煤慢速热解实验结果并结合热解反应机理和经验公式,以产物为导向构建富油煤热解反应体系,利用经典热力学分析方法进行反应体系的热力学计算,得到富油煤热解过程的化学反应热,再结合热解过程中的物理吸热量,得到了富油煤中低温慢速热解过程中的热效应。结合已报道的煤炭热解实验结果和热解热效应测定值,利用机器学习方法中的随机森林模型对煤炭热解热效应进行非线性建模和预测。结果表明:基于实验结果,以产物为导向计算得到的富油煤慢速热解热效应数值总体要低于利用TG-DSC同步联用测得的数值,误差均在10%以内。基于机器学习算法预测得到的富油煤热解热效应的预测精度达到0.9352。综合来看,所构建的2种富油煤热解热效应预测模型具有实用性和适用性。

富油煤热解过程动力学参数变化规律研究

采用非等温热重分析(TG)探究了富油煤在升温速率分别为10、20、30、40、50℃/min热解条件下的热失重规律,得到了不同升温速率下的TG-DTG曲线和表征参数。并选取富油煤热解集中温度区间(290℃~650℃)进行热解动力学分析,对比KAS法、FWO法和Friedman法3种热动力学模型计算富油煤热分解时的反应活化能。结果得到:在290℃~650℃内,富油煤的失重率为24%~29%,为主要失重区间;随着升温速率的提高,传热迟滞现象更严重,富油煤热解逐渐向高温区推进;随着转化率的增加,3种热动力学模型计算所得的反应活化能值也随之增加。其中KAS法与Friedman法的反应活化能值较为接近,FWO法求得的反应活化能值最大。

新疆和丰煤的组成结构特征与解聚技术研究进展

综述了和丰煤组成结构、萃取/热溶和热解技术的研究进展。和丰煤的碳骨架结构主要由脂肪碳和芳香碳组成。含氧官能团主要包含羟基和羰基,氮元素以吡啶氮和吡咯氮的存在形式为主,有机硫主要以噻吩和亚砜的形式存在。煤中易解离小分子化合物主要由芳烃、烷烃、烯烃、酯和醇类化合物组成。低碳烷醇能够选择性的破坏煤中的含氧桥键,有利于从煤中分离含氧类化合物。在温和条件下可以利用萃取/热溶提取技术从和丰煤中提取缩合芳烃和含氧化合物等高附加值化学品。溶胀预处理对和丰煤的热解具有促进作用,但溶胀受溶剂类型、成本等因素制约,难以实现工业化应用。某些负载型催化剂和含金属阳离子的盐类化合物在一定程度上能够抑制和丰煤热解焦油的产生,促进煤中重质组分的分解,提高煤焦油的品质。和丰煤的化学组成结构、共价键的类型、含氧官能团和杂原子的存在形式仍不清晰,热解机理以及热解焦油产物的调控还需进一步研究。

高硫煤热解过程中硫迁移规律及脱硫后焦炭特性研究

高硫炼焦煤是当前焦化行业应用较为广泛的配煤原料之一,掌握高硫煤热解过程中各形态硫的迁移规律可针对性地控制其在热转化过程中的硫排放。对4种不同煤化度的高硫煤在热解过程中的硫迁移规律进行研究,并选取2种脱硫剂来探究脱硫剂含量与高硫煤脱硫效率的关系,再通过2 kg焦炉试验用以考察添加脱硫剂对焦炭热态性能的影响。结果表明,随着热解过程的持续进行,4种高硫煤中的各形态硫含量均呈现降低趋势,其中1/3焦煤LL和肥煤SF在1000℃时脱硫效率均在44%以上。浸渍H_(3)BO_(3)和MgCl_(2)会提高炼焦煤的脱硫效率,其中H_(3)BO_(3)对热解过程中炼焦煤脱硫能力的提升尤为明显,肥煤SF、焦煤XY在H_(3)BO_(3)含量分别为3%、3.5%时的脱硫效率最高,脱硫效率分别为52.9%、39.6%。在炼焦煤中添加一定比例H_(3)BO_(3),会改善焦炭的热态性能以及提高焦炭的反应后强度,同时对焦炭的成块性能和气孔结构带来负面影响,但MgCl_(2)中镁离子对碳溶损反应的催化作用则使肥煤SF和焦煤XY的焦炭粒焦反应性升高以及反应后强度降低。

煤在H_2/Ar电弧等离子体中的热解

煤在电弧等离子体中的化学反应极其复杂 ,受到多种因素的影响和制约 .对宝德煤在电弧等离子体射流中热解反应的研究表明 ,随着煤比焓的增加 ,煤的转化率增加 ;随着煤在射流中的浓度增加乙炔的产量增加但乙炔的收率却在减小 .提出了煤在电弧等离子体射流的化学反应机理模型 ,并进行了数学推导 ,合理解释了实验现象 。

热等离子体裂解煤一步法制乙炔关键技术及过程经济性分析

热等离子体裂解煤一步法制乙炔过程为煤的直接化工利用提供了一条绿色、清洁和高效率的转化途径。基于兆瓦级热等离子体裂解煤反应器的研发,概述了已有的基础和工程研究成果,并重点从高效气固混合、结焦控制以及反应器优化与放大3个方面探讨了反应器的一些关键技术问题。从反应系统角度出发,基于对该过程的物料、能量衡算和经济效益分析结果,指出能量和物料的综合利用是该过程经济性的保证。

热等离子体裂解煤制乙炔的研究进展

热等离子体裂解煤制乙炔过程为煤的直接化工利用提供了一条有前景的、清洁的转化途径,有望成为替代传统的电石法乙炔生产工艺的新技术。本文对等离子体煤裂解制乙炔的实验室及工业中试研究进行了评述,综述了该过程在反应体系热力学分析、实验室和工业中试规模实验研究以及产物气急冷技术等方面的研究进展,分析了该过程在工业化进程中尚存在的关键性问题,提出有待深入开展的基础研究方向。

褐煤热破裂的显微CT实验

采用μCT225kVFCB型高精度显微CT试验系统并配以微型气氛炉,研究了内蒙古平庄褐煤热破裂随温度的变化关系。研究结果表明,褐煤在100℃左右时,大裂隙（〉800μm）占主导地位;200℃左右时,中等裂隙（100~400μm）占主导地位;300℃之后微裂隙（〈100μm）占主导地位;热破裂的阈值为300℃左右;在300℃之前孔隙裂隙的产生发展主要是因为热破裂,300℃之后,微裂隙和孔隙的产生主要是因为煤体发生热解化学反应,油气逸出,固体骨架逐渐转变为半焦体。