CN114616084A - 用于交联橡胶的回收和脱硫的方法 - Google Patents

用于交联橡胶的回收和脱硫的方法 Download PDF

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CN114616084A
CN114616084A CN202080064093.8A CN202080064093A CN114616084A CN 114616084 A CN114616084 A CN 114616084A CN 202080064093 A CN202080064093 A CN 202080064093A CN 114616084 A CN114616084 A CN 114616084A
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詹弗兰科·马里斯
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Maris Fratelli SpA
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Abstract

用于硫化橡胶(10)的回收和脱硫的处理方法在设备中进行，所述设备包括：用于将硫化橡胶研磨成颗粒的研磨机(12)；脱硫双螺杆挤压机(20)，其设置有用于硫化橡胶颗粒的强制进料的装置(18)和恒温装置；布置在双螺杆挤压机(20)的下游的单螺杆挤压机(22)，其配备有恒温装置、用于脱硫橡胶的过滤器(26)和形状类似于狭槽的挤压模具(28)，脱硫橡胶以条带或片材的形式从挤压模具挤出；用于脱硫橡胶条带或片材的冷却装置。双螺杆挤压机(20)在35和450℃之间的温度下操作，螺杆的转速在15和600rpm之间，扭矩密度在11和18Nm/cm3之间，使得双螺杆挤压机(20)的整个纵向延伸的剪切率保持基本恒定。

Description

用于交联橡胶的回收和脱硫的方法
技术领域
本发明涉及用于交联橡胶的回收和脱硫的方法(process)。
背景技术
通常，待回收的橡胶由来自专门的收集中心和/或废物填埋场的工业加工废物和/或已达到使用寿命的制品组成。
硫化橡胶的分子链通常通过化学键连接，这些化学键通过横向连接硫原子的硫原子桥形成。因此，硫化橡胶具有类似于热固性聚合物的结构，不能在生产周期中重复使用。
已知向交联橡胶施加一定量的能量，比如用以断裂由硫产生的化学键，使得弹性材料返回其在硫化处理之前的初始物理化学状态，并准备好在生产循环中重复使用的设备(plant)。
然而，尽管越来越多的选择性和高性能的废物分类方法变得越来越普遍，但被收集以进行脱硫处理的橡胶通常含有污染最终获得的脱硫橡胶，从而损害其性能的其它物质的颗粒。
发明内容
因此，本发明的目的是提供一种方法，以克服由于待处理的硫化橡胶中不可避免地存在的杂质而导致的这一缺点。
该目的通过一种具有权利要求1所述特征的用于交联橡胶的回收和脱硫的方法来实现。本发明的方法的优选特征在从属于权利要求1的权利要求中描述。
本发明满足了目前市场上对脱硫橡胶的纯度的需求，使得可以进行非降解回收处理，该非降解回收处理需要减少的能量输入，并且生产出脱硫且基本上不含杂质和污染物的最终塑料材料。
附图说明
本发明的进一步的优点和特征将从下文的详细描述中变得明了，下文的详细描述通过参考附图的非限制性示例来提供，其中：
图1是用于实施本发明的方法的设备的示意性正视图，为了更清楚起见，该设备被分成两部分；
图2是图1中的设备的平面示意图；
图3是图2中的细节的放大视图；
图4是根据图1中的线IV-IV的剖视图；
图5是根据图1中的线V-V的剖视图；以及
图6是图2中的进一步细节的放大视图。
具体实施方式
一种用于硫化橡胶10的回收和脱硫的设备包括(图1和图2)用于橡胶10的研磨和脱硫的研磨机12，在所述研磨机12的下游设置有均化器14和重量/体积计量单元16，其将研磨机12中产生的橡胶颗粒供给到装置18，该装置18将所述颗粒强制供给到双螺杆脱硫挤压机20中。
双螺杆挤压机20的下游是单螺杆挤压机22，其配备有齿轮泵24、用于脱硫橡胶的过滤器26和形状类似于狭槽的挤压模具28，脱硫橡胶以条带或片材的形式从该挤压模具中挤出。
在挤压模具28的下游具有包含冷却水的罐30、脱水和干燥烘道32以及用于收集脱硫橡胶条带或片材的装置33。
强制进料装置18本身是已知的，并且允许将具有不同形状、颗粒尺寸和表观密度的硫化橡胶颗粒容易地引入到双螺杆挤压机20中。该装置通常包括料斗34和柱体36(图3)，一个或更多个具有锥形或柱形几何形状的螺杆38在所述柱体36内旋转；它相对于挤压机垂直定位(或者在未示出的实施例中横向定位)，并且可具有机械、电气或气动驱动，以便迫使硫化橡胶颗粒进入双螺杆挤压机20。这种装置18的使用增加了挤压机20的螺杆的自由体积的填充率，并且已证明在膨胀硫化橡胶的处理中特别有效，该膨胀硫化橡胶的密度通常在50至350kg/m3之间。在这种情况下，螺杆的更大程度的填充允许生产率的显著提高，即，与没有强制进料装置18的情况相比，提高超过100％，从而进一步显著降低了由于剪切应力过大而导致的橡胶的降解。
挤压机20内的剪切率(shear rate)(或几何剪切率)在其整个长度上保持恒定，使得橡胶的分子链之间的交联键断裂，从而避免硫化橡胶的可能降解。由强制进料装置18确定的挤压机20的高填充率确保在每个区域中存在恒定的材料，从而使前进以及施加的应力均匀。相反，在不存在强制进料装置18的情况下，由于被处理的材料的形状和密度，被处理的材料将在挤压机20内经受不同的剪切率，这会使其降解。同样，在从硫化橡胶到脱硫橡胶的转变中，高填充率有利于冷却，这也能够抵制降解。
此外，强制进料装置18通过允许处理具有不同颗粒尺寸的、具有在0.2mm和15mm之间的尺寸的粉末或粒的形式的颗粒而增加了设备的操作灵活性。
双螺杆挤压机20有利地包括柱形模块，所述柱形模块通常具有等于螺杆的外直径的4倍的长度，并且被串联安装以形成连续的柱体。通常，双螺杆挤压机20的长度至少等于螺杆的外直径的64倍，优选不大于螺杆的外直径的80倍。
挤压机20设置有恒温装置，该恒温装置一方面包括附接至柱体的外表面的多个电阻器，另一方面(图4)包括由多个管状孔40形成的水冷却回路，这些管状孔被实现为迷宫，其在相关柱体的壁44中围绕其中心空腔平行于挤压机的纵向轴线42延伸。通过以所需方式调节加热阶段和冷却阶段的交替，可以控制施加到弹性材料的能量，防止其在分子链之间的交联化学键的断裂后降解。
螺杆的外直径和内直径之比在1.22和1.78之间，优选在1.55和1.78之间。以本身已知且未在图中示出的方式，输送和混合元件的序列被单独地配置在螺杆的多排轴上，尤其是具有几何轮廓以使填充均匀，如在EP-1 136 228B1中所述的，这允许施加到橡胶的剪切应力以及因此由所述橡胶吸收的比能保持均匀且受控。
典型地，扭矩密度在11Nm/cm3和18Nm/cm3之间，且螺杆的旋转速度在15rpm和600rpm之间，从而确保了螺杆的高填充率，并且剪切率在挤压机20的整个长度上保持较低且恒定。最终结果是更高的生产率(最高达到40-60％)，并且相对于使用具有相似的几何参数、螺杆转速相同但扭矩密度较低的挤压机，其操作温度较低。
单螺杆挤压机22以已知方式包括柱体和机械地连接至减速器的主马达，减速器又连接至在柱体内旋转的塑化螺杆，所述塑化螺杆的长度通常等于相应螺杆直径的8至20倍。
挤压机22设置有恒温装置，该恒温装置一方面包括固定在柱体的外表面上的多个电阻器，另一方面包括水冷却回路(图5)，所述水冷却回路形成有多个管状孔46，所述管状孔形成为迷宫，其在柱体的壁50中平行于挤压机22的纵向轴线48延伸，呈在柱体的中心空腔周围的圆形冠的形式。
用于在柱体内部输送材料的螺杆可以是通过内部水循环强制冷却的类型。
挤压机22所配备的过滤器26包括传统的格栅，并且可以是半自动或自动类型，这两种类型都允许熔融材料在两个不同的通道上连续流动。不言而喻，与半自动类型不同，自动类型可确保在无操作者的技术监督的情况下的连续生产。
过滤器26的存在增加了橡胶沿挤压机22前进时遇到的阻力，导致压力增加，从而导致温度升高，这可能导致橡胶的降解。
然而，这种影响通过恒温装置，尤其是通过优选的双水冷却回路，以及由螺杆施加的混合作用来补偿，其通过逐渐使新的橡胶部分与柱体和螺杆的冷却表面接触来使温度均匀。因此，这些措施的结合成功地显著降低了脱硫橡胶的温度。
有利地，挤压机22的出口处的模具28具有可变的几何形状，从而允许以所需方式确定所挤出的脱硫橡胶条带或橡胶片材的尺寸。
该设备进一步包括用于允许脱硫橡胶从双螺杆挤压机20通行到单螺杆挤压机22的装置。特别地，图6示出了用于将双螺杆挤压机20直接连接至单螺杆挤压机22的连接元件52。
在图中未示出的本发明的替代实施例中，前述用于允许脱硫橡胶从双螺杆挤压机20通行到单螺杆挤压机22的装置可以包括：
-料斗，其收集从双螺杆挤压机20挤出的脱硫橡胶并将其给送入单螺杆挤压机22中；或者
-一对或更多对面对的压力辊，其将来自双螺杆挤压机20的脱硫橡胶条带转移入单螺杆挤压机22中。
上述的设备可用于处理基本上具有任何化学性质，并且先前用于制造任何类型的制品(比如尤其是小汽车、重型车辆和飞机的轮胎)的硫化弹性体。可脱硫的弹性体的示例为天然橡胶(NR)、丁二烯橡胶(BR)、乙丙橡胶(EPR)、丁苯橡胶(SBR)、丁腈橡胶(NBR)、三元乙丙橡胶(EPDM)、异戊二烯橡胶(IR)、氯丁橡胶(CR)、丙烯酸橡胶、硅橡胶以及聚氨酯和氯磺化聚乙烯。
应当注意的是，不得将其它物质添加到待处理的弹性体中，比如热塑性材料或工艺添加剂，因此，降低了处理成本以及与其使用相关的环境影响。
具体而言，硫化橡胶被送至研磨机12。该研磨机12将其减小成所需尺寸的颗粒，随后送至均化器14。然后将由此获得的橡胶颗粒通过分配器16引入到强制进料装置18中，该强制进料装置18将其进给到双螺杆挤压机20中。该双螺杆挤压机20执行橡胶的脱硫。
挤压机20在35℃和450℃之间的温度下操作，螺杆的转速在15rpm和600rpm之间，扭矩密度在11Nm/cm3和18Nm/cm3之间，从而实现了螺杆的高填充率和对于双螺杆挤压机的整个纵向延伸的基本恒定的剪切率。
可通过在双螺杆挤压机20的一个或更多个点54处注入水来促进材料的冷却。所述一个或更多个点54位于距初始部分(即，仅在脱硫已发生之后)等于螺杆的外直径的至少32倍的距离处。相对于处理的橡胶的量，水的注入量可在1-30％(按重量计)之间。注入的水的和随后蒸发的水，以及通过脱硫产生的其它气体成分，可通过脱气器件56(比如位于一个或更多个排放导管中的提取螺杆或抽吸泵，所述排放导管从挤压机柱体20横向分支)以本身已知的方式去除。注水点54和后续的脱气点56之间的距离优选为螺杆的外直径的4至24倍，甚至更优选为螺杆的外直径的8至16倍。
相对于在无水条件下操作，水的注入使得橡胶的温度降低约20-30℃，从而防止由温度引起的降解现象，并减少由于蒸汽对产生脱硫橡胶的气味的物质的剥离作用而产生的脱硫橡胶的气味。脱硫后立即注入水使橡胶突然冷却也具有使其门尼粘度增加约6％的效果。
然后，离开双螺杆挤压机20的脱硫橡胶被引导通过连接元件52进入单螺杆挤压机22，在所述单螺杆挤压机22中，其温度降低约15-30℃。
在通过过滤器26时，通常最初存在于待处理的橡胶中的杂质块被阻挡，从而所述橡胶得到净化，达到与原始产品相当的质量水平。
橡胶最终以条带或片材的形式被挤压通过模具28，并被浸入罐30中，以通过罐中包含的水进一步进行冷却。有利地，水可包含抗堆积添加剂。
然后，从罐30出来的条带或片材被送入干燥烘道32，最后发送至收集装置33。
当然，在不损害本发明的原理的情况下，实施方式和实施例的细节可相对于纯粹通过示例描述的内容广泛的变化，而不因此脱离如随附权利要求中限定的本发明的范围。

Claims (10)

1.一种用于通过使用设备对硫化橡胶(10)进行回收和脱硫的方法，所述设备包括：
-研磨机(12)，所述研磨机用于将所述硫化橡胶研磨成颗粒；
-双螺杆挤压机(20)，所述双螺杆挤压机用于脱硫，其设置有用于所述硫化橡胶颗粒的强制进料的装置(18)和恒温装置；
-单螺杆挤压机(22)，所述单螺杆挤压机布置在所述双螺杆挤压机(20)的下游，并设置有恒温装置、用于脱硫橡胶的过滤器(26)和形状类似于狭槽的挤出模具(28)，脱硫橡胶以条带或片材的形式从所述挤出模具中挤出；以及
-冷却装置，所述冷却装置用于去硫化橡胶的条带或片材，
其中，所述双螺杆挤压机(20)在35℃和450℃之间的温度、15rpm和600rpm之间的螺杆转速以及11Nm/cm3和18Nm/cm3之间的扭矩密度下操作，使得所述双螺杆挤压机(20)的整个纵向延伸上的剪切率保持基本恒定。
2.根据权利要求1的方法，其中，所述双螺杆挤压机(20)的螺杆的外直径和内直径之比在1.22和1.78之间，优选在1.55和1.78之间。
3.根据前述权利要求的任一项所述的方法，其中，所述双螺杆挤压机(20)的长度至少等于螺杆的外直径的64倍，优选不超过螺杆的外直径的80倍。
4.根据前述权利要求中的任一项所述的方法，其中，为了使脱硫橡胶从双螺杆挤压机(20)转移到单螺杆挤压机(22)中，所述设备进一步包括：
-连接元件(52)，所述连接元件用于将所述双螺杆挤压机(20)直接连接至单螺杆挤压机(22)；或者
-料斗，所述料斗收集从所述双螺杆挤压机(20)挤出的脱硫橡胶并将其给送入所述单螺杆挤压机(22)；或者
-至少一对面对的压力辊，所述压力辊将来自双螺杆挤压机(20)的脱硫橡胶条带转移到单螺杆挤压机(22)中。
5.根据前述权利要求中的任一项所述的方法，其中，所述模具(28)具有可变的几何形状。
6.根据前述权利要求中的任一项所述的方法，其中，所述冷却装置包括填充水的罐(30)，其中，脱硫橡胶的条带或片材被浸入所述罐中。
7.根据前述权利要求中的任一项所述的方法，其中，将水注入所述双螺杆挤压机(20)的至少一个点中，所述点位于距入口的距离等于螺杆的外直径的至少32倍的距离处。
8.根据权利要求7的方法，其中，所述双螺杆挤压机(20)设置有脱气器件，用于去除其中形成的气体和/或蒸汽。
9.根据权利要求8的方法，其中，注水点和所述脱气器件所在的后续点之间的距离在螺杆的外直径的4倍和24倍之间。
10.根据权利要求9的方法，其中，所述注水点和所述脱气器件所在的后续点之间的距离在螺杆的外直径的8倍和16倍之间。
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