CN116925799A - 一种包覆用和纺丝用各向同性沥青的制备方法 - Google Patents
一种包覆用和纺丝用各向同性沥青的制备方法 Download PDFInfo
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Classifications
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- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/16—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles according to the "fluidised-bed" technique
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- D—TEXTILES; PAPER
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D01F9/155—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from petroleum pitch
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- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明涉及一种包覆用和纺丝用各向同性沥青的制备方法，以乙烯焦油、催化裂化油浆、中低温煤焦油和生物焦油等富芳烃重质油为原料，采用沸腾床反应形式对原料进行加氢稳定和异构改性，沸腾床加氢尾油在含氧线型高分子的诱导聚合作用下得到预聚合沥青，预聚合沥青在等离子体辐射作用下进行氧化交联反应，进一步提高所得各向同性沥青产物的软化点和残炭值，并抑制中间相光学结构的生成，同时各向同性沥青产物中的分子量分布相对集中，表现出优异的包覆性能和均相熔融纺丝性能。
Description
技术领域
本发明涉及一种包覆用和纺丝用各向同性沥青的制备方法，属于高级新型炭材料制备技术领域。
背景技术
碳纤维是优异的轻量化材料，然而，碳纤维的高成本以及复杂的制造工艺极大地限制了碳纤维复合材料在汽车上的应用。因此，降低碳纤维成本成为当务之急。沥青基碳纤维质量轻、密度小、耐腐蚀性及耐磨性强、具有很高的导电导热性等，被广泛应用于超高导热材料、航空飞机制造、新型建筑加固材料、汽车构件材料、体育用品、风力发电等领域。考虑碳纤维的生产成本和力学性能，各向同性沥青基碳纤维被认为是最理想的候选材料之一。然而，获得具有优异力学性能的具有成本效益的各向同性沥青基碳纤维仍然是一个巨大的挑战。
已大规模商业化应用的锂离子电池负极材料主要是石墨类(包括天然石墨、人造石墨、MCMB)，其余如软碳、硬碳、硅/碳复合材料以及钛酸锂等尚在试验开发阶段及少量试生产。石墨类负极材料的原料主要有天然石墨、石油焦、沥青焦、针状焦以及包覆沥青。为了克服石墨本身存在的一些结构缺陷，根据不同用途需要对其进行包覆处理，减少其首次不可逆容量，提高循环性能。一般地，天然石墨类负极材料都需要进行包覆，包覆沥青具有相当大的市场。
现有技术中对制备优异性能的各向同性沥青作了不少尝试。CN116288816A公开了一种各向同性沥青基碳纤维制备方法，包括以下步骤：在氮气氛围下处理乙烯焦油，与中钢煤沥青混合溶解于苯中得到混合沥青；加入氮-溴代丁二酰亚胺在氙灯照射下机械搅拌得到溴化的混合沥青；蒸馏去除混合沥青中的苯，随后处理得到脱溴聚合沥青；熔融纺丝机制备沥青纤维；管式炉中升温先氧气后氮气得到各向同性沥青基碳纤维。CN115466626A公开了一种高品质各向同性沥青的制备方法，将溴化的甲基萘与煤沥青混合进行共炭化反应得到，采用共炭化方法来改善煤沥青的反应活性，解决了其本身不利于聚合的缺点，改善了聚合沥青的流变性能，进一步提高了合成沥青的聚合度。CN115558306A提供一种各向同性沥青材料的制备方法，基底材料与改性材料混合后通过高温搅拌处理得到，改性材料中的高分子链状结构会接枝到基底材料的芳香分子结构上，从而阻止大平面片成结构的形成，进而抑制各向异性结构材料的形成，得到了各向同性沥青材料。
发明内容
本发明的目的在于克服现有技术的不足，提供一种包覆用和纺丝用各向同性沥青的制备方法，依次采用沸腾床加氢稳定和异构改性、含氧线型高分子的诱导聚合和等离子体辐射氧化交联反应，进一步提高所得各向同性沥青产物的软化点和残炭值，并抑制中间相光学结构的生成，所得各向同性沥青产物的分子量分布相对集中，表现出优异的包覆性能和均相熔融纺丝性能。
本发明的目的是采用以下技术方案实现的：
一种包覆用和纺丝用各向同性沥青的制备方法，以乙烯焦油、催化裂化油浆、中低温煤焦油、生物焦油等富芳烃油中的一种或几种为原料油，包括如下具体步骤：
(1)原料油通过沸腾床反应模式实现加氢稳定和异构改性，得到加氢尾油；
沸腾床反应采用过渡金属/硅铝沸石基催化剂，反应温度为250-350℃，氢初压为1-8MPa，反应时间为0.5-4h；过渡金属选自铂、镍或者钼；
(2)向加氢尾油中添加含氧线型高分子进行诱导聚合反应，得到预聚合沥青；
含氧线型高分子为酚醛树脂或聚丙烯酸，添加量为加氢尾油质量的1-10wt％；
诱导聚合反应温度为150-350℃，反应时间为1-2h；
(3)预聚合沥青在氧化气体鼓泡及等离子体辐射同时作用下进行均质氧化交联反应，得到软化点为220-280℃、残炭值≥70％的包覆用和纺丝用各向同性沥青；
均质氧化交联反应温度为200-350℃，等离子体辐照剂量为10-100kGy，反应时间为1-10h；
氧化气体包括但不限于空气、氧气、臭氧/氮气混合气等，气体流量为0.5-5.0L·min-1·kg-1。
本发明中，所述步骤(1)中采用沸腾床反应形式实现加氢稳定和异构改性，在反应过程中反应器内温度更加均匀、气液固三相传质更加高效，更加适用于重质油原料体系；所述步骤(2)和(3)是相互匹配耦合的反应过程，含氧线型高分子诱导聚合反应和等离子体辐射氧化交联反应通过相互作用而彼此联合加快反应速率，降低反应条件。
在诱导聚合反应温度下，含氧线型高分子会发生热解生成大量的小分子自由基，这些自由基以夺氢的形式诱导芳烃分子活化，活化后的芳烃分子以亚甲基“桥联”的形式相结合，得到线型度较高的多环芳烃大分子，显著提升沥青分子的柔韧性，使其表现出较高的可纺性能，同时含氧线型高分子裂解产生的自由基还与沥青产物分子结合，提高芳核周围烷基侧链数量，有助于提升各向同性沥青的氧化反应活性和包覆沥青的浸润性能。
等离子体辐射氧化交联反应中，氧化气体鼓泡氧化将活化后的芳烃分子的线性亚甲基“桥联”结构变为三维，并提高芳核周围烷基侧链上含氧官能团的数量，在等离子体辐射反应中脱除芳核周围烷基侧链上含氧官能团，并产生大量自由基，自由基进一步与沥青产物分子结合，生成品质优良的各向同性沥青产物。
本发明还提供了上述制备方法得到的各向同性沥青，以及各向同性沥青在用于制备包覆沥青和纺丝沥青中的应用，所述各向同性沥青纺丝后形成的沥青基纤维原丝在300℃下进行预氧化处理，预氧化处理后在1200℃下炭化2h制得的碳纤维拉伸强度达到937-992MPa。
与现有技术相比，本发明的有益效果是：
(1)本发明涉及的原料来源丰富，自由度高；设计合理，生产工艺精密，原料处理深度高，对设备要求低，易于实现工业化。
(2)采用沸腾床加氢稳定和异构改性-含氧线型高分子的诱导聚合作用-等离子体辐射氧化交联反应，能够在氧化过程中抑制中间相光学结构的生成，各向同性沥青产物的分子量分布相对集中，软化点和残炭值得到提高，表现出优异的包覆性能和均相熔融纺丝性能。
具体实施方式
实施例1
取70wt％的乙烯焦油与30wt％的中低温煤焦油混合作为原料油，通过300℃采用铂/硅铝沸石基催化剂、氢初压2MPa、反应时间4h，原料通过沸腾床反应模式实现加氢异构改性，得到加氢尾油；向加氢尾油中添加其质量8wt％的酚醛树脂，并在反应温度310℃下进行诱导聚合反应2h，得到预聚合沥青；预聚合沥青在氧化气体鼓泡及等离子体辐射同时作用下进行均质氧化交联反应，氧化交联反应温度为330℃、等离子体辐照剂量80kGy、反应时间4h，采用的氧化性气体为空气，气体流量为4.0L·min-1·kg-1，得到软化点258℃、残炭值73％的包覆用和纺丝用各向同性沥青，纺丝后形成的沥青基纤维原丝在300℃下进行预氧化处理，预氧化处理后在1200℃下炭化2h制得的碳纤维拉伸强度达到937MPa。
实施例2
取60wt％的催化裂化油浆、20wt％％乙烯焦油和20wt％％生物焦油混合作为原料油，通过330℃采用(镍-钼)/硅铝沸石基催化剂、氢初压6MPa、反应时间1h，原料通过沸腾床反应模式实现加氢异构改性，得到加氢尾油；向加氢尾油中添加其质量6wt％的聚丙烯酸，并在反应温度200℃下进行诱导聚合反应2h，得到预聚合沥青；预聚合沥青在氧化气体鼓泡及等离子体辐射同时作用下进行均质氧化交联反应，氧化交联反应温度为270℃、等离子体辐照剂量60kGy、反应时间8h，采用的氧化性气体为氧气，气体流量为3.0L·min-1·kg-1，得到软化点为271℃、残炭值为78％的包覆用和纺丝用各向同性沥青，纺丝后形成的沥青基纤维原丝在300℃下进行预氧化处理，预氧化处理后在1200℃下炭化2h制得的碳纤维拉伸强度达到992MPa。
Claims (8)
1.一种包覆用和纺丝用各向同性沥青的制备方法，以富芳烃油为原料油，其特征在于，包括如下步骤：
(1)原料油通过沸腾床反应模式实现加氢稳定和异构改性，得到加氢尾油；沸腾床反应采用过渡金属/硅铝沸石基催化剂；
(2)向加氢尾油中添加含氧线型高分子进行诱导聚合反应，得到预聚合沥青；含氧线型高分子为酚醛树脂或聚丙烯酸；
(3)预聚合沥青在氧化气体鼓泡及等离子体辐射同时作用下进行均质氧化交联反应，得到软化点为220-280℃、残炭值≥70％的包覆用和纺丝用各向同性沥青。
2.根据权利要求1所述的一种包覆用和纺丝用各向同性沥青的制备方法，其特征在于，富芳烃油选自乙烯焦油、催化裂化油浆、中低温煤焦油或生物焦油中的一种或几种。
3.根据权利要求1所述的一种包覆用和纺丝用各向同性沥青的制备方法，其特征在于：步骤(1)中，反应温度为250-350℃，氢初压为1-8MPa，反应时间为0.5-4h；过渡金属选自铂、镍或者钼。
4.根据权利要求1所述的一种包覆用和纺丝用各向同性沥青的制备方法，其特征在于：步骤(2)中含氧线型高分子的添加量为加氢尾油质量的1-10wt％；诱导聚合反应温度为150-350℃，反应时间为1-2h。
5.根据权利要求1所述的一种包覆用和纺丝用各向同性沥青的制备方法，其特征在于：步骤(3)中均质氧化交联反应的温度为200-350℃，反应时间为1-10h，等离子体辐照剂量为10-100kGy。
6.根据权利要求1所述的一种包覆用和纺丝用各向同性沥青的制备方法，其特征在于：氧化气体选自空气、氧气、臭氧/氮气混合气中的一种，气体流量为0.5-5.0L·min-1·kg-1。
7.权利要求1-6任一所述的制备方法得到的包覆用和纺丝用各向同性沥青。
8.根据权利要求7所述的各向同性沥青，其特征在于，所述各向同性沥青纺丝后形成的沥青基纤维原丝在300℃下进行预氧化处理，预氧化处理后在1200℃下炭化2h制得的碳纤维拉伸强度达到937-992MPa。
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