CN110937575A - 石墨纤维缠绕石墨设备及其成型方法 - Google Patents
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Abstract
本发明提供了一种石墨纤维缠绕石墨设备,主体结构为石墨管、石墨炉筒或石墨塔节,主体结构或局部的外壁上具有酚醛树脂、环氧酚醛树脂或沥青树脂浸渍的石墨纤维缠绕层,所述的树脂中主要填料是石墨粉填料,石墨粉的小颗粒表面或具有抗氧化层或者镀银层。本发明的制备方法中,先在石墨粉的小颗粒表面浸涂抗氧化层烘干或者镀银层,接着作为填料添加到树脂中,然后用树脂浸渍石墨纤维缠绕石墨设备。本发明的设备具有更高的传导系数,具有极好的承压能力,热胀冷缩均匀,使用寿命长久。
Description
技术领域:
本发明涉及一种石墨设备的增强制备技术。
背景技术
石墨制造的氯化氢合成炉、石墨管或石墨塔等石墨设备具有耐腐蚀性号、耐热性高,传热效率高等优点 。但是常规的石墨合成炉等石墨设备的石墨材质脆性较大,耐气压强度偏低,其外壁需要设置钢质护壳。
然而钢质护壳与石墨材质的热膨胀系数不同,在高温下容易出现两种材质之间的分层,导致传热效果欠佳,而且钢材耐腐蚀性较差,导致设备的维护成本增大。
申请号:2012104937461的发明提供了一种水冷壁式石墨炉筒的盐酸合成炉,冷却部件包含炉筒、进水管、出汽管。石墨炉筒是由多块石墨圈拼接而成,每个石墨圈经过酚醛树脂二次浸渍后经130℃-380℃高温处理。炉筒与进水管、出汽管的连接法兰是耐热钢制成的,合成部件和吸收部件的炉壳是碳钢制成的。该发明的主体与外壳的材质差异较大,容易分层。导致传热性降低,耐压性减低。
申请号:2013101227554的发明涉及一种高分子材料焊接内胆纤维缠绕复合材料高压气瓶及其制造方法,属于液化石油气用储存装置领域。首先将金属接头放到注塑机的模具腔中进行高分子材料的注塑,形成金属接头与高分子材料紧密结合为一体的半圆球形注塑件。然后将高分子材料的长圆筒形主体放到高分子材料焊接机中央固定;再将两个半圆球形注塑件分别放入高分子材料焊接机的两端固定;启动高分子材料焊接机将长圆筒形主体两端与半圆球形注塑件一次性焊接形成密封的内胆;最后使用缠绕机在内胆外进行纤维缠绕层的缠绕。该发明的材质都是高分子材质,导入效果较差,不能作为传热设备。
发明内容
发明目的:
提供一种具有增强外壳、传热效果好、耐压强度高的石墨纤维缠绕石墨设备及其成型方法。
技术方案:
本发明的石墨纤维缠绕石墨设备,主体结构是传热用的石墨管、石墨炉或石墨塔,另在主体结构或者局部(石墨材质的局部)的外壁上具有酚醛树脂、环氧酚醛树脂或沥青树脂(这三种树脂的耐热性较好,与石墨纤维的粘接强度较高)浸渍石墨纤维的缠绕层外壳(或者在石墨管、石墨炉或石墨塔的局部具有该外壳),所述的石墨纤维是将碳纤维进行石墨化处理后获得,其导热性优于碳纤维,其热膨胀系数与石墨制品基本相同,石墨纤维与石墨同质,在热变形时热胀冷缩基本一致,缠绕纤维不会因为膨胀系数的差异导致缠绕力减弱,不会出现应力分层;而且,石墨纤维热传导系数优越于碳纤维,高于碳纤维15~20%,使得具有该缠绕层的石墨制品的壁面传热性能更好,有利于实现石墨制品壁内外空间之间的热交换。
所述的树脂中的主要填料是石墨粉填料(起填充、增强、传热等功能,进一步保证上述缠绕层的纤维增强材料和粒子增强材料都是石墨材质,使得所述的树脂固化后的热胀冷缩性能与石墨材质接近);树脂中或有少量的重质碳酸钙或轻质碳酸钙的填料,以便具有更合适的韧性,不易破碎。树脂中另有溶剂等必须的助剂。
石墨粉具有热膨胀小,导热性好、抗热震性和化学稳定性好等诸多优点,但是有一个缺点:易被氧化。
优选地,在所述的树脂中,还含有陶瓷类抗氧化剂或者银粉添加剂,分散在酚醛树脂基体中,吸附在石墨粉上,能够延缓或阻止石墨粉的氧化。
进一步优选,在所述的石墨粉颗粒表面预先设置有陶瓷类抗氧化剂涂层或者化学镀银层,然后添加到树脂基体中作为主要填料。
本发明的制备成型方法如下:
先将适量的石墨粉填料以及少量的陶瓷类抗氧化剂或银粉添加到酚醛树脂、环氧酚醛树脂或沥青树脂中,树脂中可含有其它填料和助剂;接着,用所述的树脂浸渍石墨纤维,缠绕石墨管、石墨炉或石墨塔的石墨设备外壁;然后,在合适的工艺条件下固化为石墨纤维的缠绕层外壳,成为石墨纤维缠绕的石墨设备。
所述的石墨纤维可先用硅烷偶联剂涂覆,以便增加与树脂基体的粘接力。
优选地,先将陶瓷类抗氧化剂涂覆在石墨粉的小颗粒表面、烘干,在石墨粉颗粒表面形成薄薄的抗氧化层,既不影响石墨质传热,同时提高了该缠绕层树脂基体的耐温性能,又避免了石墨粉被氧化。接着将石墨粉作为填料添加到所述的树脂中。
或者优选地,先在石墨粉的小颗粒表面制作镀银层,其制作方式:将石墨粉浸入在多巴胺(二羟基苯丙氨酸)水溶液中,于室温条件下进行搅拌,多巴胺通过氧化聚合交联并沉积在石墨粉表面,进行化学镀银,虽然该制作过程工序较多,但能更好地避免石墨粉的氧化,且使得石墨粉的导热性能更好。接着将该石墨粉作为填料添加到所述的树脂中。
有益效果:
本发明的石墨制品,具有极好的抗爆抗压的力学性能,具有良好的传热性能;内层石墨材质与外壳层的材质热胀冷缩系数接近,随温度变化不容易产生热应力开裂,使得压力传递更好,承压能力更好;设备的维护成本降低,使用寿命长久。
附图说明
图1是本发明的一种石墨设备(合成氯化氢石墨炉)的纵向剖面结构示意图;
图中:1—灯头座; 2—石墨炉底; 3—水冷石墨炉筒; 4—合成段钢管束或石墨筒体(石墨筒体的外壁也可具有上述的缠绕层外壳);5—氯化氢出口气室; 6-石墨纤维缠绕层;7-石墨换热块;8—上封头。
Ⅰ段—合成段;Ⅱ段—取热段;Ⅲ段—冷却段;Ⅳ段—炉顶。
具体实施方式
如图1所示的石墨纤维缠绕石墨炉,主体结构是传热用的石墨炉体。自下而上具有合成段(合成氯化氢气体)、取热段(回收反应热)、冷却段(冷却氯化氢气体)、炉顶(合成炉炉盖)。合成段具有灯头座1、石墨材质炉底2、水冷石墨炉筒3,取热段具有用于产生并输送蒸汽的合成段钢管束或石墨筒体4,冷却段具有氯化氢出口气室5和多块叠置的石墨换热块6,炉顶段具有石墨材质的上封头8。
另在石墨炉体的冷却段的石墨换热块6的外壁上具有酚醛树脂浸渍石墨纤维的缠绕层外壳7。
所述的酚醛树脂中的主要填料是石墨粉填料,或有少量的轻质碳酸钙填料。
所述的石墨粉的小颗粒表面具有陶瓷类抗氧化剂涂层。
本发明的石墨纤维缠绕石墨炉制备方法如下:首先制作和装配石墨炉的主体结构。接着,将陶瓷类抗氧化剂涂覆在石墨粉的小颗粒表面、烘干,将所述的石墨粉作为填料添加到酚醛树脂中;所述的树脂中再添加少量的轻质碳酸钙填料和其它必须的助剂;然后用所述的树脂浸渍石墨纤维,缠绕在石墨炉的冷却段的石墨换热块6的外壁上;最后在合适的工艺条件下固化,在石墨换热块6的外壁上具有了石墨纤维的缠绕层外壳,使得整个石墨炉成为导热效果好、力学强度高的石墨纤维缠绕的石墨设备。
Claims (6)
1.一种石墨纤维缠绕石墨设备,主体结构是传热用的石墨管、石墨炉或石墨塔,其特征在于:主体结构或者局部的外壁上具有酚醛树脂、环氧酚醛树脂或沥青树脂浸渍石墨纤维的缠绕层外壳。
2.根据权利要求1所述的石墨纤维缠绕石墨设备,其特征在于:所述的树脂中的主要填料是石墨粉填料,或有少量的重质碳酸钙或轻质碳酸钙的填料。
3.根据权利要求1或2所述的石墨纤维缠绕石墨设备,其特征在于:所述的树脂中,还含有陶瓷类抗氧化剂或者银粉添加剂。
4.根据权利要求2所述的石墨纤维缠绕石墨设备,其特征在于:所述的石墨粉颗粒表面具有陶瓷类抗氧化剂涂层或者化学镀银层。
5.一种权利要求1所述的石墨纤维缠绕石墨设备的成型方法,其特征在于:
先将适量的石墨粉填料,以及少量的陶瓷类抗氧化剂或银粉添加到酚醛树脂、环氧酚醛树脂或沥青树脂中;所述的树脂中可含有其它填料和助剂;接着用所述的树脂浸渍石墨纤维,缠绕石墨管、石墨炉或石墨塔的石墨设备外壁;然后在合适的工艺条件下固化为石墨纤维的缠绕层外壳,成为石墨纤维缠绕的石墨设备。
6.根据权利要求5石墨纤维缠绕石墨设备的成型方法,其特征在于:先将陶瓷类抗氧化剂涂覆在石墨粉的小颗粒表面、烘干,或者先在石墨粉的小颗粒表面制作镀银层;接着,将所述的石墨粉作为填料添加到所述的树脂中。
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