Cho Jong Hoon, Im Ji Sun
C1 Gas & Carbon Convergent Research, Korea Research Institute of Chemical Technology (KRICT), Daejeon 34114, Republic of Korea.
Department of Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon 34134, Republic of Korea.
ACS Omega. 2022 Feb 23;7(9):7845-7852. doi: 10.1021/acsomega.1c06750. eCollection 2022 Mar 8.
The present study focused on the development of a binder pitch to allow for low-temperature forming processes when fabricating coke-based artificial graphite blocks while increasing the density of the resultant blocks. To this end, high-softening-point (200 °C) pitches were fabricated. The pitch and byproducts obtained from the pitch synthesis were then used as binders to fabricate blocks with high mechanical strength and low porosity. Pitches were fabricated using pyrolyzed fuel oil (PFO), a petroleum residue. A high-softening-point (200 °C) pitch synthesized at 420 °C for 3 h was used as a binder pitch, and conventional pitch (124 °C) was synthesized at 400 °C for 1 h and then used. Pitch byproducts were extracted according to the boiling point of naphthalene (two rings) and anthracene (three rings) with varying numbers of aromatic rings by distillation. The largest amount of pitch byproduct was obtained in the temperature range from 220 to 340 °C, and the content of naphthalene in the byproduct was the highest over the entire temperature range. The fabricated pitches at 420 °C and byproducts were mixed to form modified pitches. It was found that their softening point and coking value (CV) decreased with the increasing content of the pitch byproduct. Low-boiling point components of the byproducts were removed from the modified pitches at the kneading process temperature (200 °C), and the mass-loss rate observed in the carbonization process temperature range (200-900 °C) was comparable to that of the high-softening-point pitch. The kneading rate of the pitch and byproduct was determined and selected based on the mass-loss rate described above, and blocks were then fabricated using a hot press. Subsequently, the fabricated blocks were subjected to heat treatment for carbonization (900 °C) and graphitization (2700 °C). After the heat treatment, the true density and apparent density of the blocks were measured, and the porosity of the blocks was calculated based on these values. The porosity of the graphite block fabricated using the pitch with a softening point of 120 °C was 21.84%, while the porosity of the graphite block fabricated using the modified pitch was 14.9%. For mechanical strength analysis, their compressive strength was measured. The compressive strength of the graphite block made of the conventional pitch (CP) was measured to be 47.59 MPa, while the compressive strength of the graphite block made of pitch mixed with a byproduct distilled at 220-340 °C was 58.79 MPa. This result suggested that a decrease in the porosity resulted in increased mechanical strength. The application of the modified pitches developed in the present study temporarily decreased the softening point of the high-softening-point pitch due to the effect of the added byproducts, allowing for a low-temperature forming process. It was also possible to fabricate artificial graphite blocks with low porosity due to the high CV of the high-softening-point pitch. As a result, blocks with high mechanical strength could be obtained.
本研究着重于开发一种粘结剂沥青,以便在制造焦炭基人造石墨块时实现低温成型工艺,同时提高所得块体的密度。为此,制备了高软化点(200℃)的沥青。然后将沥青及其合成过程中产生的副产物用作粘结剂,来制造具有高机械强度和低孔隙率的块体。沥青是使用热解燃料油(PFO)——一种石油残渣来制备的。在420℃下合成3小时得到的高软化点(200℃)沥青用作粘结剂沥青,而常规沥青(124℃)在400℃下合成1小时后使用。通过蒸馏,根据萘(二环)和蒽(三环)等具有不同芳环数的物质的沸点来提取沥青副产物。在220至340℃的温度范围内获得的沥青副产物量最大,并且在整个温度范围内,副产物中萘的含量最高。将在420℃制备的沥青与副产物混合以形成改性沥青。发现它们的软化点和焦化值(CV)随着沥青副产物含量的增加而降低。在捏合工艺温度(200℃)下,从改性沥青中去除副产物的低沸点成分,并且在碳化工艺温度范围(200 - 900℃)内观察到的质量损失率与高软化点沥青相当。根据上述质量损失率确定并选择沥青与副产物的捏合比例,然后使用热压机制造块体。随后,对制造的块体进行碳化(900℃)和石墨化(2700℃)热处理。热处理后,测量块体的真密度和表观密度,并基于这些值计算块体的孔隙率。使用软化点为120℃的沥青制造的石墨块的孔隙率为21.84%,而使用改性沥青制造的石墨块的孔隙率为14.9%。对于机械强度分析,测量它们的抗压强度。由常规沥青(CP)制成的石墨块的抗压强度测得为47.59MPa,而由与在220 - 340℃蒸馏的副产物混合的沥青制成 的石墨块的抗压强度为58.79MPa。该结果表明孔隙率的降低导致机械强度增加。本研究中开发的改性沥青的应用由于添加副产物的作用,暂时降低了高软化点沥青的软化点,从而实现了低温成型工艺。由于高软化点沥青的高CV,还能够制造低孔隙率的人造石墨块。结果,可以获得具有高机械强度的块体。