Preparation of Activated Carbon Functional Ceramics From Coal Pitch

The influences of different impregnation temperatures,pre-oxidation,carbonization temperatures and activation conditions on the iodine value and carbon deviations was discussed.SEM,EDS,and BET techniques were used to investigate the microstructures and properties of materials.Results showed that activated carbon functional ceramic exhibited excellent comprehensive properties when porous ceramics adsorbed the coal pitch at 150 ℃ for 0.5 h,oxidized at 420 ℃ for 1.0 h,and carbonizated at 700 ℃ for 1.0 h and then activated by using KOH（20wt%） as agent at 800 ℃ for 1.0 h,as confirmed by the high iodine value（162.6 mg/g） and high specific surface area（83.5 m2/g）.

In-situ carbonizing of coal pitch on the surface of silica sphere as quasi-graphitized carbon stationary phase for liquid chromatography

A novel chromatography stationary phase with a quasi-graphitized carbon modified shell has been developed. Coal pitch was directly carbonized on the surface of porous silica with in-situ carbonization. The carbonized coal pitch coating exhibits some degree of graphitization with a 78 nm-thick layer on the surface of silica and a 0.5 nm-thick layer on the inner surface of the mesopores. Based on the special structure of the graphitized carbon coating, the novel stationary phase can provide multiple interactions such as hydrophobic interaction, π-π interaction and dipole-dipole interaction. The novel composite material exhibited unique separation selectivity and excellent separation efficiency for polar compounds, including imidazoles, nucleosides and pesticides. Besides, the packed column also exhibited great repeatability with the RSDs of the retention time of nucleosides between 0.07%-0.50%(n = 5). Finally, satisfied result was achieved in the separation of fullerenes on the new column, suggesting the great potential in the industrial-scale purification of fullerenes.

Preparation of pitch precursor with excellent spinnability for general-purpose carbon fibre using coal tar pitch as raw material

Tetrahydrofuran(THF) extract of coal tar pitch(CTP) was used instead of blending CTP with pretreated pyrolysis fuel oil to prepare an isotropic pitch precursor with excellent spinnability for general-purpose carbon fibre through bromination-dehydrobromination. The feasibility and effectiveness of synthesising an isotropic pitch precursor derived from THF-soluble(CTP-THFs) is demonstrated in this study.The results show that CTP-THFs contains more light components than CTP;CTP-THFs and CTP monomer proportions were 62.52% and 45.32%, respectively. However, based on comparisons of CTP-THFsBr0 and CTPBr0 characterisations, CTP-THFs exhibits better polycondensation than CTP. Bromination-dehydrobro mination promotes polycondensation of pitch precursors, leading to greater carbon aromaticity in CTP-THFsBr5, CTP-THFsBr10, and CTP-THFsBr15 than that in CTP-THFsBr0 and CTPBr0. CTP-THFsBr5 and CTP-THFsBr10 have excellent spinnability even with softening points as high as 230 ℃. The pericondensed carbon and carbon aromaticity of CTP-THFsBr5 and CTP-THFsBr10 are high owing to the higher degree of polycondensation;however, they still possess a more linear molecular structure. The as-prepared carbon fibre exhibits homogeneity and uniformity, and the mechanical performance is comparable with that of commercial general-purpose carbon fibre products.

Feasibility Investigation of Bitumen Properties by Blending of Coal Tar Pitch

There are numerous methods and additives available to improve the durability and quality of road bitumen. A coal tar obtained by coal coking was distilled in a laboratory into fractions of initial boiling point IBP-180℃ (gasoline-like fuel), 180℃ - 360℃ (diesel-like fuel), and >360℃ (residue or coal tar pitch). The coal tar pitch was added into road bitumen by up to 1 - 5 wt% and investigated the alteration of physical and chemical properties. The physico-mechanical properties of coal tar pitch and bitumen blends, as well as the chemical group composition, were determined using standard techniques (MNS) and the SARA method, respectively. Results of 3% coal tar pitch addition into bitumen enhanced ductility by 12.4% and softening point by 1.6℃. We found that blending with bitumen coal tar pitch as a modifier could improve bitumen properties.

Porous carbon nanofibers derived from low-softening-point coal pitch towards all-carbon potassium ion hybrid capacitors

Potassium ion hybrid capacitors(PIHC)have promising applications in medium and large-scale energy storage systems due to their high energy/power density,abundant potassium resource and low cost.However,the slow kinetics of battery-type anodes originating from the large-size K+results in a mismatch between the two electrodes,rendering the modest energy density of PIHC.Herein,we first develop an electrospinning strategy to successfully synthesize fibrous precursor by using the HNO_(3)pre-oxidized low-softening-point coal pitch as the low-cost raw material.With further carbonization or KOH activation,the two types of carbon nanofibers(CNF)are fabricated as anode and cathode materials,respectively,towards the dual-carbon PIHC devices.Thanks to its threedimensional interconnected porous conducting network and large layer spacing,the resulted CNF anode material is endowed with high reversible capacities,excellent rate and long cycle stability.Meanwhile,the activated CNF cathode with a large surface area of 2169 m^(2)·g^(-1)exhibits excellent capacitive performance.A PIHC constructed with the two fibrous electrodes delivers an energy density of110.0 Wh·kg^(-1)at 200.0 W kg^(-1),along with a capacitance retention of 83.5%after 10,000 cycles at 1.0 A·g^(-1).The contribution here provides a cost-efficiency avenue and platform for advanced dual-carbon PIHC.

Mesophase formation of coal-tar pitches used for impregnant of C/C composites

By a polarized light optical microscopy with a hot stage, liquid phase nuclear magnetic resonance 13 C NMR and 1 H NMR, X ray diffractometry and scanning electron microscopy (SEM), the factors that affect the formation of mesophase in C/C composites, such as pressure, quinoline insolubles (QI) and heterocylic compounds, were analyzed. Further, the graphitizability of the resultant carbon was discussed. The results indicate that to some degree, QI contents accelerate the formation of mesophase at atmospheric pressure; while at high pressure, the coalescence and growth of mesophase spherules are impeded and the resultant coke produced from higher QI content pitch is harder to be graphitized. This is in agreement with the transfer of microstructure from domain anisotropy to fine grained mosaics.

Study of oxidization of coal–pitch by O_3

For the purpose of obtaining small molecular and oxygen-containing aromatic compounds,taking a toluene-extracted coal pitch as the research object,the oxidation of coal–pitch by ozone(O_3) in formic acid was studied.The coal–pitch sample and the oxidized pitch residue were characterized by elementary analysis and Fourier transform infrared spectroscopy(FTIR),while the small molecular products were analyzed by a gas chromatography–mass spectrometer(GC–MS).The results show that the highest oxygen content of oxidized coal pitch had been acquired at a reaction temperature of 50 °C,an O_3 flow rate of6300 mg/h and a reaction time of 4 h.Quite a lot of hydroxyls and carbonyls were introduced into the structure of the oxidized coal–pitch,while the small molecules produced mainly involve nonpolar aromatic compounds,aromatic anhydride and quinone compounds.It is speculated that the mechanism is direct electrophilic oxidation in which the molecules of O_3 directly attack the aromatic ring at its carbon atoms with high electron density,and then generate hydroxyl or carbonyl until the aromatic ring cracks.This study shows that O_3 can make the fused aromatic ring of coal–pitch become oxidized and depolymerized,and hence the ozonization of coal–pitch can be a potential method for obtaining oxygencontaining aromatic compounds.

Carbon foams prepared from coal tar pitch for building thermal insulation material with low cost

A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. The physical and chemical performance of high softening point pitch(HSPP) can be regulated by vacuumizing owing to the cooperation of vacuumizing and polycondensation. Results indicate that the optimum softening point and weight ratio of quinoline insoluble are about 292℃ and 65.7%, respectively. And the optimum viscosity of HSPP during the foaming process is distributed in the range of 1000-10000 Pa·s. The resultant carbon foam exhibits excellent performance, such as uniform pore structure, high compressive strength(4.7 MPa), low thermal conductivity(0.07 W·m^(-1) ·K^(-1)), specially, it cannot be fired under the high temperature of 1200 ℃.Thus, this kind of carbon foam is a potential candidate for thermal insulation material applied in energy saving building.

Comparative Study of the Modification of Coal Tar Pitch for Higher Carbonization Yield and Better Properties

Parent coal tar pitch(CTP)was modified with boric acid(BA),cinnamaldehyde(CMA)and the mixture of BA and CMA,respectively.The parent CTP and three modified CTPs were characterized by elemental analysis,thermogravimetric analysis,Fourier transform infrared(FT-IR)spectroscopy and scanning electron microscopy.The four samples were carbonized at different temperatures and resultant carbonized products were characterized by FT-IR spectroscopy,X-ray diffraction and polarized-light microscopy.The results show that the morphologies and carbonization behaviors of the parent CTP and modified CTPs are quite different.The carbonization yield of the CTP modified with the mixture of BA and CMA is higher than that of CTP modified with BA or CMA only.In addition,the modification of CTP with 7 g of BA and 10 ml of CMA results in an increase in carbonization yield by5.64%.During the pyrolysis of modified CTPs,the dehydration of BA or the distillation of CMA occurs at the temperature lower than 300°C,and methyl and methylene groups of the modified CTPs disappear gradually as temperature rises.Furthermore,the modification of CTP by the mixture of BA and CMA results in more intensive mesophase spheres than other modified CTPs,and the modified CTP is easier to be carbonized to form graphitic carbon.

Characterization of Coal Tar Pitch and Paving Pitch by UV,EA and NMR

In order to enlarge the use of coal tar pitch(CTP) in paving road,CTP and 60th paving pitch (PP) were extracted by n-heptane,toluene and ethanol step by step in a Soxhlet apparatus.The three fractions of CTP and PP were detected using UV-absorption(UV-A),elemental analyses(EA) and nuclear magnetic resonance(NMR) firstly as a whole unit after quality characterization of physical nature of CTP and PP were finished.The CTP had more saturate aliphatic and residue compounds dissolved in ethanol.On the other hand there were more continental type structures of aromatic ring than that of PP.There was almost no residue in PP after extracted by ethanol.The results explained why CTP was crisp in cold winter and was soften in summer.The following research will focus on how to change the chemical construction of CTP into the relative similar structures with those of PP through adding polymer.

大倾角煤层伪俯斜工作面平行四边形液压支架结构设计与运动响应

液压支架是大倾角煤层伪俯斜工作面“围岩-装备”系统稳定性的核心,现有液压支架结构无法适应伪俯斜开采空间稳定性要求,严重影响了该类条件下工作面安全高效开采。以大倾角煤层伪俯斜开采工作面为研究背景,采用工程类比、结构运动学分析、数值仿真的综合研究方法,分析了大倾角伪俯斜工作面“支架-围岩”稳定性特征,并以ZY7000/22/45型液压支架为基础,发明一种新型平行四边形液压支架,进行了结构合理性设计,分析了关键构件运动学响应特征。研究表明:大倾角伪俯斜综采工作面垮落矸石非均匀填充以及矸石对支架的砸、压、推作用是影响支架稳定性的关键因素,平行四边形顶梁与底座更适应伪俯斜工作面。设计的平行四边形支架顶梁、底座及立柱排布方式为平行四边形,异形掩护梁与后连杆、油缸连杆、底座构成柔性四连杆结构。平行四边形支架立柱为主要承载结构,油缸连杆为主要运动机构,其运动特征影响因素主要为上下柱窝间距和前后连杆与掩护梁铰接位置间距,其中掩护梁与后连杆是支架位姿调控的关键,且支架运动过程中无双扭线产生。研究结果为该类条件工作面支架提供了一种选型,一定程度上保障了该类煤层的安全生产。

煤沥青交联改性处理对碳结构的影响

沥青基炭制品的碳结构高度依赖前驱体沥青的性质。采用化学交联的方法对沥青进行改性处理时,尽管化学交联的反应机理为亲电取代反应,但交联剂、催化剂的种类不同,沥青改性程度存在差异,进而影响炭制品结构。以中低温煤沥青为原料,探索3种交联剂(对苯二甲醇(PXG)、苯甲醛(BA)、对苯二甲酰氯(TPC))、5种催化剂(对甲苯磺酸、浓硫酸、浓硝酸、浓盐酸、硼酸)对沥青交联改性后炭制品结构的影响。通过TG-DTG、FT-IR研究交联改性后沥青热稳定性及沥青官能团的变化;借助XRD、Raman表征改性后沥青炭制品的微观结构差异。结果表明:交联剂和催化剂的存在促进了沥青分子的交联,有效阻止了热转化过程中轻组分挥发,提高了沥青的结焦值、软化点、热稳定等指标。以PXG为交联剂,沥青支链上亚甲基CH_(2)的H不易被取代;而以硼酸为催化剂时,支链末端甲基上的H易被取代;以BA为交联剂,取代氢的位置明显发生在芳香环上;以TPC为交联剂、浓硫酸为催化剂时,交联产品的C=0官能团含量增加,说明在这种组合下,TPC参加反应较多。无论与哪种交联剂相结合,浓盐酸为催化剂时,交联反应更易促进苯环上和支链上的C—H键发生取代反应。经过交联改性后的沥青,炭化过程中分子间较强的π-π相互作用减弱,有效阻止碳有序结构的形成,碳无序结构含量I_(D)/I_(G)增大。同时碳微晶层间距d_(002)明显增加,有序堆积平均堆积高度L_(c)减小,芳香层数降低,说明化学交联不仅影响有序碳结构排列,还可抑制碳微晶结构发育。其中硼酸作为催化剂时,催化效果更理想。获得的炭制品d_(002)在同组产品中最大。PXG、硼酸组合与沥青发生交联时,所得碳材料的d_(002)达0.377 nm。本研究为进一步定向调控和构筑沥青基碳材料奠定基础。

沥青基多孔炭材料制备及其双电层储能性能

多孔炭作为超级电容器电极的主要材料,具有导电性好、化学稳定性高、工作温度范围广等优点。以内蒙古煤沥青(CTP)为原料,分别以K_(2)CO_(3)和KOH为活化剂,通过化学活化法制备多孔炭材料,优化制备工艺并比较2种活化剂制备的多孔炭在结构和电化学性能方面的差异。结果表明,K_(2)CO_(3)活化和KOH活化最佳制备条件均为活化温度700℃、活化时间60 min、活化剂与CTP质量比为2∶1。2种活化剂制备的多孔炭在微观结构上有很大差异,KOH活化所得多孔炭(PH-T700)表面平整光滑并分布大量规则的圆孔,而K_(2)CO_(3)活化所得多孔炭(PC-T700)内部呈层叠交错的珊瑚状结构。与PH-T700相比,PC-T700具有更多中孔,离子扩散阻力更小。在1 A/g电流密度下,PC-T700和PH-T700的比电容量分别为252.90和261.02 F/g,PC-T700和PH-T700组装成纽扣型对称电容器,0.5 A/g时比电容量分别为226.01和225.51 F/g,且PC-T700表现出更优秀的倍率性能和循环稳定性。5000次充放电后,PC-T700和PH-T700的比电容量分别为初始值的103.77%和98.20%。输出功率达1038.46 W/kg时,PC-T700能量密度仍保持7.5 Wh/kg,实际使用价值高于PH-T700。

碳纳米管模板导向制备煤沥青基电热材料及其性能调控研究

本研究以煤沥青为原料、多壁碳纳米管为结构导向剂,通过炭化制备了形貌和结构可控的煤沥青基碳膜,考察了多壁碳纳米管对导电填料结构及碳膜电热性能的影响规律。研究发现,多壁碳纳米管掺杂导致导电填料的晶格排列有序度增加、晶格间距减小和石墨化程度提高;多壁碳纳米管的引入提高了碳膜的载流子浓度,进而显著提高了其导电性。掺杂2%碳纳米管,可使煤沥青基碳膜的载流子浓度提高3.2倍、电阻降低67%;在5、10和15 V电压下,煤沥青基碳膜的发热温度分别可达44、88和165℃,相对未掺杂碳膜分别提高了7、22和70℃,显示出极大的应用前景。

氢氧化镁-硼酸锌复合阻燃剂辅助制备产率高和电容性能优异的煤焦油沥青基多孔碳

以煤焦油沥青为前驱体,氢氧化镁-硼酸锌复合阻燃剂为助剂,直接在空气条件下高温碳化制备了煤沥青基多孔碳,并探究其电化学性能。得益于阻燃剂的阻燃协同其活化、掺杂功能化作用,得到了高产率(55.1%)、多原子(N、B、O)掺杂且具有分级多孔结构的多孔碳。将其作为超级电容器电极材料,在三电极体系中0.5 A·g^(-1)电流密度下比电容可达344 F·g^(-1)。此外,以制备的多孔碳和壳聚糖基氨基酸质子盐凝胶电解质组装的柔性对称电容器具有29.3 Wh·kg^(-1)的高能量密度,在50 000次循环后电容保持率为96.9%,且在-25~75℃温度区间内可正常工作,显示出宽的温度使用范围。

改性木质素磺酸钠在煤沥青水浆中的性能研究

为提高煤沥青利用率,以LS(木质素磺酸钠)为主要原料,经磺甲基化和缩合反应后合成MLS(改性木质素磺酸钠)分散剂,用于制备煤沥青水浆。采用FTIR(红外光谱)、XRD(X射线衍射)和表面张力分析了MLS的结构及性质,采用响应曲面法考察其最佳制备条件,并研究浆体的分散稳定性。结果表明MLS分散剂的最佳制备条件为:磺甲基化试剂质量分数12%,甲醛质量分数18%,尿素质量分数10%,反应温度80℃,反应时间4 h。当MLS质量分数为0.5%时,最大制浆质量分数达到54.83%,而LS的最大制浆质量分数仅为51.44%。且MLS分散剂制备的浆体,属于屈服假塑性流体,符合Herschel-Bulkley模型,屈服应力较小。静置5 d后,LS和MLS制备的浆体析水率分别为3.45%和2.30%,说明MLS的降黏增稳能力较强,利于提高煤沥青水浆的工业应用。

超级电容器用活性炭的研究进展

简述了超级电容器的工作原理和超级电容炭的市场情况,分析了植物类、石油焦类、树脂类不同原料制备电容炭(无定型粉末炭)的性能特点及制备工艺,介绍了煤焦油沥青基球形活性炭和煤液化沥青球形活性炭的研究进展,对比了无定型粉末活性炭与球形活性炭的性能优劣,最后对煤液化沥青球形活性炭用于超级电容器的优势及推广应用进行了展望。

神华煤液化沥青离心脱灰行为的影响因素研究

利用煤液化沥青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沥青的高效深度脱灰。以焦化洗油和神华煤液化沥青在热萃取釜中制备的热萃取液为研究对象,借助旋转黏度仪考察了1∶1,4∶1,6∶1三种剂渣比(焦化洗油与神华煤液化沥青的质量比)体系黏度随温度(20℃,40℃,60℃,80℃,100℃)的变化规律,探究了影响煤液化沥青灰分脱除和上层离心液收率的离心转速(1000 r/min,1500 r/min,2000 r/min,2500 r/min,3000 r/min,3500 r/min,4000 r/min)、剂渣比(1∶1,2∶1,3∶1,4∶1,5∶1,6∶1)和离心时间(5 min,10 min,15 min,20 min,25 min)三大行为因素,解析了神华煤液化沥青中灰分在焦化洗油混合体系中的粒度分布和形貌特征。结果表明:焦化洗油和神华煤液化沥青混合体系呈现出明显的高黏温正比特性,升高温度可显著减小不同剂渣比体系之间的黏度差异,焦化洗油和神华煤液化沥青萃取体系离心脱灰最佳工作参数为剂渣比4∶1、离心转速3000 r/min、离心时间15 min,此条件下灰分可降至0.06%,上层离心液收率可达75%。离心分离后灰分分布均匀,微观形貌呈现出不规则的锯齿层状堆叠特征,在焦化洗油和神华煤液化沥青混合体系中呈纳米级粒径分布是其不能深度脱除的根源,因此,可开发新型液相重力涡流、静电分离、沉降助剂法等技术并与离心技术相耦合,以期满足下游高端炭材料制备技术的指标要求,为煤炭直接液化技术规模化的发展和产业链的延伸提供技术支持。

中低温煤焦油沥青组分的热解特性及动力学研究

中低温煤焦油沥青(MLP)为人造炭材料的重要原料,研究其组分的热解特性及动力学对高品质中低温煤焦油沥青基炭材料的制备具有重要意义。以中低温煤焦油沥青为原料,分别采用正丁醇(BA)和二甲基亚砜(DMSO)为萃取剂以获得4种沥青组分,通过热重分析仪对中低温煤焦油沥青和4种族组分的热解行为进行研究,利用Flynn-Wall-Ozawa法、Kissinger-Akahira-Sunose法和Satava-Sestak法计算热解活化能以及热解动力学参数。结果表明:MLP、DMSOS、BAI组分的热解反应机理符合随机成核及其后续增长模型,最佳热解机理函数分别为G(α)=[-ln(1-α)]^(4/3)、G(α)=[-ln(1-α)]^(4)、G(α)=[-ln(1-α)]2,活化能分别为73.99、180.20、46.09 kJ/mol,lg A分别为5.82、13.57、3.32;BAS组分的热解反应机理符合二维扩散模型,最佳热解机理函数为G(α)=α+(1-α)ln(1-α),E=85.36 kJ/mol,lg A=6.18;DMSOI组分的热解反应机理符合二维扩散或三维扩散模型,最佳热解机理函数为G(α)=[1-(1-α)^(1/3)]^(2),E=64.42 kJ/mol,lg A=4.00。