CN112062586A - 一种环保含碳砖的生产方法 - Google Patents

一种环保含碳砖的生产方法 Download PDF

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CN112062586A
CN112062586A CN202011016480.2A CN202011016480A CN112062586A CN 112062586 A CN112062586 A CN 112062586A CN 202011016480 A CN202011016480 A CN 202011016480A CN 112062586 A CN112062586 A CN 112062586A
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田守信
申娟娟
贺恒星
柯占龙
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YANGGU XINMIN REFRACTORY MATERIALS CO Ltd
SHANDONG KEXIN NEW MATERIALS CO Ltd
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Abstract

本发明公开了一种环保含碳砖的生产方法，以镁砂、高铝、刚玉、石墨和再生耐火材料为主要原料，添加少量添加剂，以一定颗粒配比进行配料，外加碳素结合剂2.5~10%，进行混料，然后成型制得含碳砖坯。在一定条件下进行固化和炭化。炭化是在炭化窑中进行的。为了让结合剂充分热解，炭化温度为应大于5000C。炭化过程碳素结合剂热解出来的可燃气体，经过密闭管道进入燃烧室燃烧。这种工艺生产的包括镁炭砖在内的含碳砖，因有机结合剂已经热解和炭化，所以在使用过程中不会再产生有害的气体。并且在生产过程中热解产生的还原气体得到了充分燃烧，而没有放出有害气体。因此，生产和使用都是环保的，这种含碳砖具有非常好的环保价值。

Description

一种环保含碳砖的生产方法
技术领域
本发明涉及耐火材料领域，具体是一种环保含碳砖的生产方法。
背景技术
除了铝碳质连铸用整体塞棒、长水口和浸入式水口外，一般含碳砖，包括铝炭砖、镁炭砖、镁钙碳砖、铝镁炭砖等都属于不烧砖。采用镁砂、镁钙砂、氧化铝、石墨和一定量添加物等按照一定比例配制起来的。添加一定量的结合剂，混合均匀后，高压成型和150～250℃固化完成的不烧制品。到目前为止所用的结合剂都是碳素结合剂。碳素结合剂包括沥青、煤焦油、沥青改性树脂、酚醛树脂、呋喃树脂等有机结合剂。在含碳不烧砖的制造以及在用户使用过程中，这些结合剂的有机溶剂挥发和树脂热解和炭化都放出有臭味的有机物气体，特别是在用户烘烤冶金设备的过程中，不但放出这些有臭味的有机气体，污染环境，特别是煤沥青系结合剂放出苯并芘这种致癌物质，更严重影响人类的身体健康。为了降低这种结合剂对环境的影响，日本人报道过减少对环境危害的含碳砖。他们报道结果也只是减少而已，不是消除。从他们报道看，也可能是调整结合剂粘度，少加一些以减少污染量。因此没有真正消除对环境的影响。也有用无机结合剂进行结合含碳砖的，但是性能显著降低。根本不能达到目前含碳砖的使用性能。为实现环保，对不烧含碳砖，采取了减少碳含量，不用沥青，少用树脂和250℃较高温固化温度。这些只是减少了有害气体的产生量，对环境污染的减轻，不是真正解决环保问题。同时降低了含碳砖的韧性，显著降低了含碳砖的热震稳定性。在现场使用烘烤过程中，产生高温有机气体，严重影响了环境，影响了人类的健康。
发明专利CN201510292633.9报道了一种环保型镁炭砖及其生产方法。其实只是在配方里添加了环保型的超高温沥青。这不能说是环保型镁炭砖。有很多镁炭砖配方里，就没有添加沥青。真正影响镁炭砖环保性能的是结合剂酚醛树脂。这没有改变。还有一些专利是从环保的角度说是环保型的镁炭砖。主要是因为他们从用后镁炭砖提取镁炭砖原料而生产的镁炭砖。即从用后镁炭砖废弃的角度来讲，成为了环保型镁炭砖。实际上，这应该叫做再生镁炭砖为好。
我们发明了一种方法是：还原炭化，使不烧含碳砖内的有机气体全部放出来，通过节能型窑，通过燃烧法把它们全部燃烧变成CO2，H2O等无害气体排放。这样在使用过程中，就不会产生任何气体了，达到了生产厂家和用户都环保的目的。
发明内容
针对不烧含碳砖在生产和使用过程中产生的环境污染问题，发明了解决方法。即这种产品经过配料成型砖坯后，进入封闭窑进行高温炭化。在炭化过程中产生的有危害环境和健康的气体，如苯并芘、芳香族化合物、苯酚、甲醛等气体，经过封闭管道输送到燃烧室烧掉，使之变成CO2和H2O，消除了产品制造公司内部对环境污染的影响。炭化温度大于500℃，就不再有害气体产生了。因此在钢铁厂等用户使用过程中就不会产生有臭味的甲醛、苯酚、芳香族化合物等有害气体了，更不会产生致癌物质苯并芘。
具体的，本发明采用以下技术方案：
一种环保含碳砖的生产方法，包括如下步骤：
(1)以镁砂、高铝料、石墨和再生耐火材料为主要原料，添加少量添加剂，以一定颗粒配比进行配料，外加碳素结合剂2.5～10％，进行混料，然后成型制得含碳砖坯；
(2)将上述所得的含碳砖坯，在炭化窑中以一定升温速度进行固化和炭化；炭化温度为大于500℃；
(3)炭化过程碳素结合剂热解出来的还原气体，经过密闭管道进入燃烧室燃烧。
上述一种环保含碳砖的生产方法，所述镁砂为电熔镁砂或烧结镁砂，所述高铝料指的是烧结高铝矾土或刚玉，所述再生耐火材料指的是用后的镁炭砖料，铝炭砖料，铝镁炭砖料或镁钙炭砖料的一种或多种。
上述一种环保含碳砖的生产方法，所述添加剂指的是B4C、SiC、B、Zn、Al、Si之一或组合，其加入量0～4％。
上述一种环保含碳砖的生产方法，所述碳素结合剂指的是酚醛树脂结合剂，沥青，沥青改性树脂结合剂，呋喃树脂和有机硅树脂结合剂之一或组合，优选沥青改性树脂结合剂。
上述一种环保含碳砖的生产方法，配比指的是致密化的颗粒配比，即>3mm：15～25％，3～1mm:25～35％，1～0.074mm:12～30％，<0.074mm：18～30％。
上述一种环保含碳砖的生产方法，步骤(2)一定的升温速度指进行固化和炭化，具体为：
常温～100℃：升温速度：20～30℃/h，100℃保温1～5h；
100～150℃：升温速度：15～20℃/h，150℃，保温2～5h；
150～250℃：升温速度：20～30℃/h，250℃保温4～10h；
250～700℃，升温速度：50℃/h，700℃，保温10h。
上述一种环保含碳砖的生产方法，所述炭化窑采用封闭窑，且在窑的4个角和顶砖表面放入一定量的炭黑，其炭黑总量(克)为窑容积(M3)的100倍以上。
本申请的有益效果是：
1.使用及生产过程中无任何毒害气体释放，密封性能好，连接牢固，质量有保证且对环境无任何污染；
2.在该产品制造过程中，避开价格昂贵的酚醛树脂结合剂，而使用以沥青为主的改性沥青系结合剂。该结合剂成本低廉，高温石墨化性能好，比酚醛树脂有更好的使用性能。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
实施例
按照下表的配方进行配料，在混料机内混料20分钟后，出料成型。成型后按照不同的固化和炭化制度进行处理。得到的环保含碳砖见下表。
Figure BDA0002699242270000031
Figure BDA0002699242270000041
由实施例可知，经过改进工艺技术路线，解决了含碳砖的环保问题，在使用过程中不会对环境产生任何不利的影响，变成了环境友好型的产品，抗氧化性得到了改善。
从上述表格可以看出，当含碳砖仅进行200℃*12h的热处理后，使用时砖会产生大量的有害气体，如苯并芘、芳香族化合物、苯酚、甲醛等气体，苯并芘可达200ppm，对人体和环境造成伤害；但是经过对现有工艺路线的改进，当含碳砖在200℃*12h热处理后，再继续500℃*10h或者1000℃*10h进行烘烤，虽然在烘烤过程中会产生危害环境和健康的气体，但是产生的有害气体经过封闭管道输送到燃烧室烧掉，使之变成CO2和H2O，消除了产品制造对环境的污染，而且在使用时也不会产生任何有害气体。所以，通过对现有工艺的改进，不仅解决了含碳砖生产厂家在烘烤过程中对环境和人体的损害，而且就使用厂家而言，也不会对环境和人体产生任何不利影响，属于环保型的含碳砖制备工艺。

Claims (7)

1.一种环保含碳砖的生产方法，其特征在于，包括如下步骤：
（1）以镁砂、高铝料、石墨和再生耐火材料为主要原料，添加少量添加剂，以一定颗粒配比进行配料，外加碳素结合剂2.5~10%，进行混料，然后成型制得含碳砖坯；
（2）将上述所得的含碳砖坯，在炭化窑中以一定升温速度进行固化和炭化；炭化温度为大于500℃；
（3）炭化过程碳素结合剂热解出来的还原气体，经过密闭管道进入燃烧室燃烧。
2.如权利要求1所述的一种环保含碳砖的生产方法，其特征在于，所述镁砂为电熔镁砂或烧结镁砂，所述高铝料指的是烧结高铝矾土和刚玉，所述再生耐火材料指的是用后的镁炭砖料，铝炭砖料，铝镁炭砖料或镁钙炭砖料的一种或多种。
3.如权利要求1所述的一种环保含碳砖的生产方法，其特征在于，所述添加剂指的是B4C、SiC、B、Zn、Al、Si之一或组合，其加入量0~4%。
4.如权利要求1所述的一种环保含碳砖的生产方法，其特征在于，所述碳素结合剂指的是酚醛树脂结合剂，沥青，沥青改性树脂结合剂，呋喃树脂和有机硅树脂结合剂之一或组合，优选沥青改性树脂结合剂。
5.如权利要求1所述的一种环保含碳砖的生产方法，其特征在于，配比指的是致密化的颗粒配比，即>3mm：15~25%，3~1mm:25~35%，1~0.074mm:12~30%，<0.074mm：18~30%。
6.如权利要求1所述的一种环保含碳砖的生产方法，其特征在于，步骤（2）一定的升温速度指进行固化和炭化，具体为：
常温~100℃：升温速度：20~30℃/h，100℃保温1~5h；
100~150℃：升温速度：15~20℃/h，150℃，保温2~5h；
150~250℃：升温速度：20~30oC/h，250℃保温4~10h；
250~700℃，升温速度：50℃/h，700℃，保温10h。
7.如权利要求1所述的一种环保含碳砖的生产方法，其特征在于，所述炭化窑采用封闭窑，且在窑的4个角和顶砖表面放入一定量的炭黑，其炭黑总量（克）为窑容积（M3）的100倍以上。
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