CN106544759B - 一种石油沥青基碳纤维的制备方法 - Google Patents
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
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Abstract
本发明涉及一种石油沥青基碳纤维的制备方法,包括以下步骤:(1)以催化油浆为原料;(2)高压加氢预处理,氢气压力12~18MPa、反应温度420~450℃、反应1~3h,得加氢产物;(3)减压蒸馏得400~550℃的馏分,加入催化剂(1:1的Lewis酸功能化离子液体/BF3复合催化剂,Lewis酸功能化离子液体为氯铝酸类离子液体([BMIM]Cl/AlCl3)或氯化锌类离子液体(ZnCl2/PPh3C6H13Br)或氯化铁类离子液体([BMIM]Cl/FeCl3)),在惰性气体或氮气气氛中,反应压力1~8MPa、反应温度280~360℃、反应1~8h,催化缩聚得中间相沥青。(4)中间相沥青熔融纺丝,得到石油沥青基碳纤维。
Description
技术领域
本发明涉及一种石油沥青基碳纤维的制备方法,具体为一种以催化油浆为原料经高压加氢预处理、催化缩聚制得中间相沥青后,通过熔融纺丝制备石油沥青基碳纤维的方法,属于高级新型碳材料制备技术领域。
背景技术
石油沥青基碳纤维的研究始于20世纪50年代,日本在60年代末实现了工业化。1970年美国联合碳化物公司以石油沥青为原料成功制备沥青基碳纤维,1982年投入工业化。20世纪末,世界沥青基碳纤维的生产能力达到500吨/年。此后,各国加紧对沥青基碳纤维的应用研究,提高了产品性能,且开发出多种新品种,如低模量型、中模量型、航空航天级碳纤维等。我国对沥青基碳纤维的研制已有40年历史,但碳纤维产业发展缓慢,现阶段包括聚丙烯腈(PAM)基碳纤维在内,国内生产总量大约仅有2000吨/年,生产线运行状况都不太理想,且质量仍处于较低水平,严重制约了我国尖端科技和复合材料的发展。
现阶段用于生产碳纤维的沥青大多数是带有烷基侧链的稠环芳烃化合物和杂环化合物的混合物,其结构和化学组成非常复杂。在生产碳纤维之前,必须进行调制和改性预处理,制备成软化点在250℃以上的高软化点沥青。
中间相沥青又名为光学各向异性沥青,是由沥青中大分子沿分子层面方向进行平行排列,形成类似于近晶型液晶的聚集态结构。其是以普通沥青、重质油、煤焦油等为原料经热缩聚反应制得,或以芳香化合物如萘等为原料经催化缩合而成的相对分子质量为370~2000的扁盘状稠环芳烃组成的混合物。中间相沥青一般具有较高的纯度和芳香度,其特有的取向排列芳香大分子片层结构使其具有优异的物理化学性能,具有光学各向异性、热稳定性、氧化活性、可纺性以及碳化收率高等优点。以中间相沥青为原料,因其分子结构呈各向异性,可用于制备高性能碳材料,如超高模量纤维、超导热材料、超活性炭、高级复合材料、高级氟碳材料、高级电池电极等。这些高级碳材料将在国防工业、航空航天、尖端科技、日常生活等众多领域发挥巨大的作用,因此中间相沥青的研究备受关注。
利用催化缩聚法制备出中间相沥青具有中间相含量高、分子量适中、结构适宜、质量稳定等优点,并且由于催化缩聚过程中形成环烷结构,使中间相沥青具有较低的软化点、较高的溶解性和反应性,可在较短时间内进行沥青原丝的氧化稳定化,制备出高模量沥青基碳纤维。Mochida等使用AlCl3作为催化剂从萘和乙烯焦油中成功制得高可溶性中间相沥青,但AlCl3很难完全被除去,不能重复使用。Korai等以芳香烃为原料使用HF/BF3作催化剂制得了可纺性的中间相沥青,并且HF/BF3催化剂可通过常压蒸馏从沥青中移除,然后循环使用,现已实现工业化。山西煤化所以固体超强酸催化剂ZrO2/SO4 2-体系催化改性萘制得结构良好、软化点较低的中间相沥青,但是在反应过程中容易结焦。但是催化缩聚法对原料的性质要求较高,一般以纯芳烃为原料。
尽管碳纤维由于其优越的性能而被广泛应用,但其制造成本过高,中间相产率较低以及技术过于复杂等缺陷制约着碳纤维产业的发展。
发明内容
本发明操作简单,制备出高中间相含量可纺性好中间相沥青,继而制备出性能优异的石油沥青级碳纤维,提高了催化剂利用率,安全环保无污染,降低了生产成本。
本发明的石油沥青基碳纤维的制备方法包含以下步骤:(1)以催化油浆为原料;(2)高压加氢预处理,氢气压力12~18MPa、反应温度420~450℃、反应1~3h,得加氢产物;(3)减压蒸馏得400~550℃馏分,加入催化剂,在惰性气体或氮气气氛下,反应压力1~8MPa、反应温度280~360℃、反应1~8h,催化缩聚得中间相沥青;(4)中间相沥青熔融纺丝,得到石油沥青基碳纤维。
本发明更具体的采取以下技术方案:(1)以催化油浆为原料,高压加氢预处理,氢气压力12~18MPa、反应温度420~450℃、反应1~3h,得加氢产物;(2)按要求安装减压蒸馏装置,检查装置气密性,将加氢产物加入圆底烧瓶中,不要超过烧瓶的一半,加入沸石,连接真空系统,开启真空泵,当达到所要求的压力且稳定后,开始加热,升温速率维持在3~5℃/min,根据此压力下常温400℃和550℃对应的减压蒸馏温度,用接收瓶接取此温度段的馏分;(3)减压蒸馏分离得到加氢产物中400~550℃馏分,加入催化剂,在惰性气体或氮气气氛中,反应压力1~8MPa、反应温度280~360℃、反应1~8h,催化缩聚得到中间相沥青;(4)中间相沥青熔融纺丝,经过预氧化、碳化、石墨化,得到石油沥青基碳纤维。
步骤(2)中加入3~4粒沸石。
其中所述步骤(1)原料催化油浆,密度大,H/C比低,含有较多的芳香分子(芳烃含量25wt%~55wt%),芳香环数多以3~4环为主。
所述步骤(3)中的催化剂是Lewis酸功能化离子液体与BF3复合,Lewis酸功能化离子液体为氯铝酸类离子液体([BMIM]Cl/AlCl3)或氯化锌类离子液体(ZnCl2/PPh3C6H13Br)或氯化铁类离子液体([BMIM]Cl/FeCl3)。两者比例为0.5~2:1,优选为1:1,催化剂与原料的质量比为0.01~0.05。
制备得到的中间相沥青中间相含量≥95%、软化点220~260℃、H/C比0.3~0.6。
石油沥青基碳纤维,其密度为1.65~1.75g/cm3g/cm3,拉伸强度为1500~2000Mpa,拉伸模量为300~450GPa。
本发明采取的方法属于高压加氢-催化缩聚组合工艺。
高压加氢过程中,原料中芳香分加氢部分饱和,引入了环烷基结构,反应体系流动性变好,作为溶剂和供氢体限制芳烃大分子的过度缩聚,使体系的分子量趋于均匀化。由于加氢预处理阶段氢的引入减弱了π电子共轭体系,同时环烷结构增大了体系空间位阻,减弱分子间力,避免后续缩聚过程中过度缩合。
Lewis酸功能化离子液体/BF3复合催化剂是新型高效催化剂。Lewis酸功能化离子液体属于离子液体,与传统的有机溶剂相比,离子液体在较宽的温度范围内可保持良好的物理和化学稳定性,并且其蒸汽压低,不易挥发,解决了VOC环境污染问题;同时能够良好的溶解大量的无机和有机物质,且具有溶剂和催化剂的双重功能。Lewis酸功能化离子液体具有酸性,可以用来替代传统液体酸来催化石油芳烃制备中间相沥青,基于非脱氢反应机理,在较低的反应温度下,Lewis酸功能化离子液体与芳烃可形成较弱的π络合物,经过重排,生成碳正离子,促进氢转移反应,并抑制脱氢速率,在反应之初引入环烷基团同时脱除过量的脂肪侧链,使得反应体系中含有较多的环烷基和烷基结构,从而使制备得到中间相沥青的既具有高各向异性,又具有较低的软化点和较高的可溶性。BF3酸性强,亲核性弱、体积大适合做引发剂。因此Lewis酸功能化离子液体/BF3复合催化剂是理想的催化剂。
本发明与已有制备方法相比有益效果是:
(1)本发明涉及的原料无腐蚀性,来源广泛,价格低廉,经济性好。
(2)本发明所用的催化剂物理和化学性质稳定,绿色环保,对环境无污染;且具有溶剂和催化剂双重功能,活性高选择性好。
(3)采用高压加氢-催化缩聚组合工艺。高压加氢改善了原料的结构组成和分布,引入了环烷结构,提高流动性;催化缩聚反应条件温和,且使制备的中间相沥青既具有高各向异性,又具有较低的软化点和较高的可溶性,进而可制备出高品质石油沥青基碳纤维。本发明生产工艺过程环境清洁,操作简单,对设备要求低,易于推广实现工业化。
具体实施方式
下面结合实施例进一步叙述本发明所提供的以催化油浆为原料制备石油沥青基碳纤维的方法。
实施例1:
(1)催化油浆200g加入不锈钢高压釜中,氮气吹扫3次置换空气,氢气吹扫3次升压至13MPa,2℃/min升温至100℃,启动搅拌,升温至420℃反应3h,得到加氢产物;(2)按要求安装减压蒸馏装置,所有的磨口仪器接口部分都必须用真空封脂涂抹。仪器安装好后,检查装置气密性,确认装置不漏气以后,将加氢产物加入圆底烧瓶中,不要超过烧瓶的一半,加入3~4粒沸石,连接真空系统,开启真空泵,压力达到1.0mmHg且稳定后,开始加热,升温速率维持在4℃/min,查阅常减压温度对照表,找出此压力下常温400℃对应的减压蒸馏温度为192℃,550℃对应的减压蒸馏温度317℃,用接收瓶接取此温度段的馏分;(3)减压蒸馏分离得到加氢产物中400~550℃馏分,取该馏分180g加入不锈钢高压釜,向其中加入1.8g催化剂[BMIM]Cl/AlCl3/BF3,氮气吹扫3次,通氮气升压至4MPa,反应温度360℃,匀速搅拌反应2h,得到中间相沥青(95%光学各向异性,软化点240℃,H/C为0.42,残炭值为88.43%);(4)所得中间相沥青进行熔融纺丝,经预氧化、碳化、石墨化,得到优质的石油沥青基碳纤维,其密度1.69g/cm3,拉伸强度为1580Mpa,拉伸模量为315GPa。
中间相沥青的光学结构和含量通过偏光显微镜观察得到;软化点采用常规针入法测试;H/C采用元素分析仪测定;残炭采用传统电炉法测定(SH/T0170-92);纤维密度测试用Ultrapycnometer1000密度仪;拉伸强度和拉伸模量测定采用岛津AG-IS(1kN)万能材料试验机。
实施例2:
(1)催化油浆200g加入不锈钢高压釜中,氮气吹扫3次置换空气,氢气吹扫3次升压至14MPa,2.5℃/min升温至100℃,启动搅拌,升温至430℃反应2h,得到加氢产物;(2)按要求安装减压蒸馏装置,所有的磨口仪器接口部分都必须用真空封脂涂抹。仪器安装好后,检查装置气密性,确认装置不漏气以后,将加氢产物加入圆底烧瓶中,不要超过烧瓶的一半,加入3~4粒沸石,连接真空系统,开启真空泵,压力达到0.9mmHg且稳定后,开始加热,升温速率维持在4℃/min,查阅常减压温度对照表,找出此压力下常温400℃对应的减压蒸馏温度为189.8℃,550℃对应的减压蒸馏温度314.7℃,用接收瓶接取此温度段的馏分;(3)减压蒸馏分离得到加氢产物中400~550℃馏分,取该馏分180g加入不锈钢高压釜,向其中加入3.6g催化剂ZnCl2/PPh3C6H13Br/BF3,氮气吹扫3次,通氮气升压至5MPa,反应温度340℃,匀速搅拌反应4h,得到中间相沥青(98%光学各向异性,软化点246℃,H/C为0.38,残炭值为89.27%);(4)所得中间相沥青进行熔融纺丝,经预氧化、碳化、石墨化,得到优质的石油沥青基碳纤维,其密度1.65g/cm3,拉伸强度为1640Mpa,拉伸模量为306GPa。
实施例3:
(1)催化油浆200g加入不锈钢高压釜中,氮气吹扫3次置换空气,氢气吹扫3次升压至16MPa,3℃/min升温至100℃,启动搅拌,升温至440℃反应1.5h,得到加氢产物;(2)按要求安装减压蒸馏装置,所有的磨口仪器接口部分都必须用真空封脂涂抹。仪器安装好后,检查装置气密性,确认装置不漏气以后,将加氢产物加入圆底烧瓶中,不要超过烧瓶的一半,加入3~4粒沸石,连接真空系统,开启真空泵,压力达到1.0mmHg且稳定后,开始加热,升温速率维持在4℃/min,查阅常减压温度对照表,找出此压力下常温400℃对应的减压蒸馏温度为192℃,550℃对应的减压蒸馏温度317℃,用接收瓶接取此温度段的馏分;(3)减压蒸馏分离得到加氢产物中400~550℃馏分,取该馏分180g加入不锈钢高压釜,向其中加入5.4g催化剂[BMIM]Cl/FeCl3/BF3,氮气吹扫3次,通氮气升压至7MPa,反应温度320℃,匀速搅拌反应6h,得到中间相沥青(97%光学各向异性,软化点232℃,H/C为0.46,残炭值为85.06%);(4)所得中间相沥青进行熔融纺丝,经预氧化、碳化、石墨化,得到优质的石油沥青基碳纤维,其密度1.73g/cm3,拉伸强度为1720Mpa,拉伸模量为322GPa。
实施例4:
(1)催化油浆200g加入不锈钢高压釜中,氮气吹扫3次置换空气,氢气吹扫3次升压至18MPa,2℃/min升温至100℃,启动搅拌,升温至450℃反应1h,得到加氢产物;(2)按要求安装减压蒸馏装置,所有的磨口仪器接口部分都必须用真空封脂涂抹。仪器安装好后,检查装置气密性,确认装置不漏气以后,将加氢产物加入圆底烧瓶中,不要超过烧瓶的一半,加入3~4粒沸石,连接真空系统,开启真空泵,压力达到0.9mmHg且稳定后,开始加热,升温速率维持在4℃/min,查阅常减压温度对照表,找出此压力下常温400℃对应的减压蒸馏温度为189.8℃,550℃对应的减压蒸馏温度314.7℃,用接收瓶接取此温度段的馏分;(3)减压蒸馏分离得到加氢产物中400~550℃馏分,取该馏分180g加入不锈钢高压釜,向其中加入7.2g催化剂ZnCl2/PPh3C6H13Br/BF3,氮气吹扫3次,通氮气升压至8MPa,反应温度280℃,匀速搅拌反应8h,得到中间相沥青(99%光学各向异性,软化点228℃,H/C为0.51,残炭值为84.35%);(4)所得中间相沥青进行熔融纺丝,经预氧化、碳化、石墨化,得到优质的石油沥青基碳纤维,其密度1.75g/cm3,拉伸强度为1680Mpa,拉伸模量为328GPa。
Claims (4)
1.一种石油沥青基碳纤维的制备方法,包含以下步骤:(1)以催化油浆为原料;(2)高压加氢预处理,氢气压力12~18 MPa、反应温度420~450 ℃、反应1~3 h,得加氢产物;(3)减压蒸馏得400~550 ℃馏分,加入催化剂,在惰性气体或氮气气氛下,反应压力1~8 MPa、反应温度280~360 ℃、反应1~8 h,催化缩聚得中间相沥青;其中催化剂为Lewis酸功能化离子液体与BF3复合,两者比例为1:1,催化剂与原料的质量比为0.01~0.05,所述Lewis酸功能化离子液体为氯铝酸类离子液体或氯化锌类离子液体或氯化铁类离子液体;(4)中间相沥青熔融纺丝,得到石油沥青基碳纤维。
2.根据权利要求1所述的一种石油沥青基碳纤维的制备方法,其特征在于:所述催化油浆芳烃含量25 wt%~55 wt%,芳香环数多以3~4 环为主。
3.根据权利要求1所述的一种石油沥青基碳纤维的制备方法,其特征在于:所述步骤(3)中间相沥青的中间相含量≥95%、软化点220~260 ℃、H/C比0.3~0.6。
4.根据权利要求1所述的一种石油沥青基碳纤维的制备方法,其特征在于:所述步骤(4)石油沥青基碳纤维的密度为1.65~1.75 g/cm3,拉伸强度为1500~2000 Mpa,拉伸模量为300~450 GPa。
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