CN106457206A - 活性炭过滤器制品及其制备方法和应用 - Google Patents
活性炭过滤器制品及其制备方法和应用 Download PDFInfo
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- CN106457206A CN106457206A CN201580028202.XA CN201580028202A CN106457206A CN 106457206 A CN106457206 A CN 106457206A CN 201580028202 A CN201580028202 A CN 201580028202A CN 106457206 A CN106457206 A CN 106457206A
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Abstract
一种制备如本文所定义的活性炭蜂窝过滤器制品的方法,所述方法包括:挤出批料混合物来形成挤出的蜂窝体,所述批料包含:活性炭粉末;第一有机粘合剂粉末;流变学增塑液体;多孔无机粘合剂粉末;挤出助剂;和通过追加的水,干燥挤出的蜂窝体;和热处理干燥的蜂窝体。还披露一种蜂窝过滤器制品,其具有:活性炭;多孔无机粘合剂;950m2/g‑1600m2/g的BET表面积;50‑2000cpsi的孔道密度;和0.5‑0.8g/cm3的密度。
Description
本申请根据35U.S.C.§119要求2014年05月28日提交的美国临时申请系列第62/003,671号的优先权,本文以该申请的内容为基础并通过参考将其完整地结合于此。
本文所述的出版物、专利和专利文献的全文内容通过参考结合于本文。
背景
本发明涉及活性炭过滤器制品及其制备方法和应用。
概述
在一些实施方式中,本发明提供活性炭过滤器制品及其制备方法和应用。
附图简述
在本发明的实施方式中:
图1显示示例性活性蜂窝炭过滤器制品的等距视图,其具有例如约50-2000孔道/平方英寸(cpsi)的孔道密度。
图2显示图1的制品的等距视图,其具有堵塞的相邻通道。
具体描述
下面将参考附图(如果有)详细描述本发明的各种实施方式。对各种实施方式的参考不限制本发明的范围,本发明范围仅受所附权利要求书的范围的限制。此外,在本说明书中列出的任何实施例都不是限制性的,且仅列出要求保护的本发明的诸多可能实施方式中的一些实施方式。
定义
在本文所述的活性炭过滤器制品的语境中,“高活性”指吸附能力具有下述中的一种或多种:高表面积,例如950-1600m2/g的表面积;以及在挤出的过滤器制品中存在的反应性或相互作用官能团的种类和数目。吸附能力或活性可通过标准方法来定量,例如碘值(通过1克的活性炭吸附的毫克的碘)。
“包括”、“包含”或类似术语意为包括但不限于,即内含而非排它。
用来描述本发明实施方式的修饰例如组合物中成分的量、浓度、体积、加工温度、加工时间、产量、流速、压力、粘度等数值及它们的范围或者组分的尺寸等数值以及它们的范围的“约”指数量的变化,可发生在例如:制备材料、组合物、复合物、浓缩物、组分零件、制品制造或应用制剂的典型测定和处理步骤中;这些步骤中的无意误差;制造、来源或用来实施所述方法的原料或成分的纯度方面的差异中;以及类似考虑因素中。术语“约”还包括由于具有特定初始浓度或混合物的组合物或制剂的老化而不同的量,以及由于混合或加工具有特定初始浓度或混合物的组合物或制剂而不同的量。
“任选的”或“任选地”意指随后描述的事件或情况可能发生或可能不发生,描述内容包括事件或情况发生的场合以及事件或情况没有发生的场合。
除非另外说明,否则,本文所用的不定冠词“一个”或“一种”及其相应的定冠词“该”表示至少一(个/种),或者一(个/种)或多(个/种)。
可采用本领域普通技术人员熟知的缩写(例如,表示小时的“h”或“hr”,表示克的“g”或“gm”,表示毫升的“mL”,表示室温的“rt”,表示纳米的“nm”以及类似缩写)。
在组分、成分、添加剂、尺度、条件、时间和类似方面公开的具体和优选的数值及其范围仅用于说明,它们不排除其他限定数值或限定范围内的其他数值。本发明的组合物和方法可包括本文所述的任何数值或数值、具体数值、更具体的数值和优选数值的任何组合,包括明示或暗示的中间值和范围。
“包括”、“包含”或类似术语意为包括但不限于,即内含而非排它。
过去,活性炭已用于例如除去碘、彩色颜料和各种催化功能。但是,在最近几年随着活性炭处理能力的推进,活性炭的应用已显著增加。活性炭现在在从流体(即,液体或气体)流除去杂质中具有广泛应用。例如,使用活性炭可成功地过滤食物、果汁和酒精饮料中的杂质。类似地,活性炭可用于除去以较低浓度存在于空气或气体流中的气态物质,例如分离过程、除去有机蒸气的过程。活性炭特别地用于吸附和纯化来自内燃机的流体排放物或加工流。
常规地,以粉末或颗粒形式来使用活性炭。在其中过滤和/或处理连续的流体的加工流流动的工艺中,不方便使用粉末化或颗粒活性炭。对于液体和泵尤其如此,其中紧密填充的碳床可导致显著的压力降。在其中在使用过程中床振动的应用(例如在汽车中)中,颗粒的磨损导致形成细颗粒,其可捕获在移动的流体中。颗粒床中的流动路径是无规的,且将因为形成细颗粒而随时间改变。这可导致吸收效率下降。对于流动系统而言,越过粉末化颗粒床的压力降较高,这导致用于泵吸的高能量成本和类似考虑。这个问题的解决方案之一是以蜂窝的形状来形成活性炭。蜂窝几何形貌具有下述优势:可用于接触的高几何形貌表面积和越过床的较低压力降。在一些工业过程中,蜂窝几何形貌是必须的。
康宁有限公司(Corning Incorporated)已开发了各种用于制备活性炭蜂窝以避免与填充碳床相关的问题的方法。在这些技术中,常用方法例如参见授予Gadkaree等的美国专利号5,510,063,其题目为“制备具有不同吸附能力的活性炭蜂窝的方法(Method ofmaking activated carbon honeycombs having varying adsorption capacities)”。所述方法涉及将碳填料材料(例如,木炭、煤、活性炭)和任选的成孔剂、挤出助剂和可交联的树脂组合挤出成生坯体,然后固化和碳化生坯体。在碳化之后,使用CO2或蒸汽(即,物理活化)来活化产品。虽然这些方法已经令人满意地用于制造用于各种应用的活性炭蜂窝结构,它们受到高成本地高温热处理步骤的阻碍。此外,所述方法还具有不能均匀地活化碳通道的不足。当蜂窝体具有比单个通道的直径更长的通道时,这是一个显著的问题。在这些情况下,在到达通道的全部长度之前,气态氧化物就被消耗了。此外,这些现有方法的批料组合物的主要成分液体酚醛树脂是昂贵的,具有环境问题(例如排放甲醛),且需要高温处理(例如,大于800℃),从而碳化和活化从其衍生的碳基质。高温处理从烧掉的酚醛树脂形成残留物,其可在所得蜂窝过滤器制品中堵塞孔和阻碍表面积。相反,本文所述的粘合剂系统不形成可在所得蜂窝过滤器制品中堵塞孔或阻碍表面积的残留物。
在一些实施方式中,本发明提供用于制备高活性活性炭蜂窝结构的挤出批料(batch)组合物,其没有或不含酚醛树脂且避免了常规制备方法中相关的高成本高温热处理步骤,例如碳化和活化。例如,本文所述的组合物可通过下述来制备:混合受控量的活性炭粉末、有机粘合剂、多孔无机粘合剂、由粉末化有机粘合剂制备的流变学增塑液体和挤出助剂。完全配制的批料的流变学提供具有低粘合性质的低粘度组合物,其促进挤出具有细孔密度(例如50-2,000cpsi,1600-2,000cpsi,包括中间值和范围)的各种蜂窝几何形貌,以及均匀和光滑的外部表面和内部表面。
本文所述的制备方法和所得过滤器制品依赖于用于批料制剂的无机粘合剂、有机粘合剂和非树脂增塑液体粘合剂组分的适当地选择和相对量。本文所述的挤出批料组合物实现低温处理挤出的体。制备的活性炭蜂窝结构可通过下述来表征,例如:优异的结构整体性;高吸附能力/单位体积;在较低成本下的方便的制造;以及在给定的碳体体积中的均匀的高活性(即,高表面积)。本文所述的活性炭和挤出的蜂窝制品的高吸附活性获自下述的至少一种:高表面积;和在活性炭的表面上存在或不存在某些官能团。
在一些实施方式中,本发明提供制备含有活性炭的过滤器制品的方法,所述方法不含碳化步骤和活化步骤。在一些实施方式中,本发明提供碳过滤器制品,其具有蜂窝结构和基于高表面积性质例如950-1600m2/g的高吸附活性,这有助于吸附。
在一些实施方式中,本发明提供挤出批料组合物和用于制备活性炭蜂窝结构的方法,所述方法不使用液体酚醛树脂,且所述方法无需高温碳化和活化。
在一些实施方式中,本发明提供可通过混合受控量的下述物质的粉末来配制的组合物:活性炭;有机粘合剂;多孔无机粘合剂;由粉末化的有机粘合剂制备的流变学增塑液体;和一种或多种任选的挤出助剂。组合预先活化的(即,预活化的碳粉末)碳原料与非树脂粘合剂实现在较低温度例如小于约250℃的温度下处理挤出的碳制品。本文所述的制备方法的一个方面使用合适的干燥的非酚醛粘合剂,将干燥的粘合剂溶解于水中来形成具有可与酚醛树脂溶液相比拟的粘度的溶液,以及组合所述溶液与无机粘合剂来形成有机粘合剂和无机粘合剂系统。增塑液体也可用作粘合剂,且与固体粘合剂(例如,有机粘合剂和无机粘合剂中的一种或两种)协同作用来在挤出后处理之后,赋予活性炭颗粒显著的粘合强度。不存在酚醛树脂以及本文所述的批料制剂中所用的有机粘合剂的较低分解温度允许在较低温度例如小于约250℃的温度下来处理挤出的体。
在一些实施方式中,本文所述的制备碳组合物的方法可包括下述总体步骤:
在环境温度例如从15-30℃,配料和挤出批料组合物来形成挤出的体;
在例如约120-160℃下在排气式(air-vented)烘箱中干燥挤出的体;和
在氮气中在例如200-250℃下热处理干燥的体来稳定蜂窝结构。
在一些实施方式中,从本文所述的组合物和方法获得的产品提供高吸附活性、活性炭蜂窝结构,其可用于各种吸附或过滤器制品和方法,包括例如水和空气净化以及挥发性烃气体储存。虽然不存在传统的高温处理步骤,但本文所述的蜂窝具有高吸附活性、高强度和高结构整体性。
在多个方面中,本发明是有优势的,包括例如:
制造能力:本文所述的挤出制备方法制备具有高蜂窝孔道密度的蜂窝过滤器制品,例如1,600-2,000孔道或通道开口/平方英寸(cpsi)。
简单和低加工温度:通过使用本文所述的组合物,可通过消除在传统制备方法中使用的碳化步骤和活化步骤,来减少在制备活性蜂窝结构的方法中所需的步骤数目;本文所述的制备方法还可在不含液体酚醛树脂的情况下来实现,不存在酚醛树脂允许在较低温度(例如,小于或等于250℃)下处理挤出的体。
均匀的活性和放大能力:本文所述的组合物和方法消除了与酚醛树脂基碳蜂窝的物理活化相关的显著问题,该问题是沿着和越过蜂窝通道不能均匀地活化(即,非均匀活化)。在本发明中,通过在蜂窝结构的壁之内和表面之上均匀地分布活性炭颗粒,来避免非均匀活化问题,这种碳颗粒分布带来在整个活性炭蜂窝体中的均匀活性。因此,对于放大该工艺用于商业生产而言,这变得完全不成问题。
成本:与酚醛树脂基活化蜂窝的制备相比,本文所述的方法和组合物存在两个显著的成本优势。第一个成本优势是消除了高成本的高温热处理步骤(即,碳化和活化),这带来劳动力和能量节省。第二个成本优势是使用低成本液体粘合剂来取代更昂贵的液体酚醛树脂,这带来能量和材料成本节省。在制备本文所述的活性炭蜂窝时,这些提供显著的操作成本益处。成本优势可提供例如与酚醛树脂基工艺相比,本文所述的活性炭蜂窝的操作生产成本下降约40%。
广泛的应用能力:根据本发明的活性炭的吸附性质实现将其用于许多应用,例如吸收的天然气储存、裂解烃,纯化工业气体、防污染装置、在食品和化学工业中的液相纯化工艺、水处理、液相回收和分离、催化剂或催化剂载体和类似的应用。
在一些实施方式中,本发明提供了一种制造活性炭蜂窝过滤器制品方法,其包括:
例如在如约15-30℃的环境温度下,挤出批料混合物来形成挤出的蜂窝体,所述批料混合物包含:
40重量%-60重量%的活性炭粉末;
5重量%-10重量%的第一有机粘合剂粉末;
20重量%-30重量%的流变学增塑液体,其由在水中的5重量%-10重量%的第二有机粘合剂粉末制备;
4重量%-15重量%的多孔无机粘合剂粉末;
1重量%-3重量%的挤出助剂;和
通过追加的50重量%-100重量%的水,
所述重量%基于排除了基于追加的水的批料成分的总重量;
在例如约120—160℃下将挤出的蜂窝体干燥1-2小时;以及
在氮气中,在例如200-250℃下将干燥的蜂窝体热处理2-4小时,从而稳定蜂窝结构,并制备活性炭蜂窝过滤器制品。
在一些实施方式中,热处理的蜂窝制品可具有950m2/g-1600m2/g的BET表面积。
在一些实施方式中,热处理的蜂窝过滤器制品可具有1,600-2,000cpsi的孔道密度。
在一些实施方式中,活性炭蜂窝过滤器制品可具有例如100-500微米、100-250微米和100-150微米的壁厚度,包括中间值和范围。用于1600cpsi活性炭蜂窝过滤器制品的一种测量的壁厚度是约150微米。
在实施方式中:
第一有机粘合剂粉末例如可选自下组:甲基纤维素、羟基丁基纤维素、乙基纤维素、羟基丁基甲基纤维素、羟基乙基纤维素、羟基甲基纤维素、羟基丙基纤维素、羟基丙基甲基纤维素、羟基乙基甲基纤维素、羧基甲基纤维素钠和类似材料,或其混合物。
第二有机粘合剂粉末例如可选自下组:羧基甲基纤维素钠、聚乙烯醇、壳聚糖和类似材料,或其混合物。
多孔无机粘合剂粉末例如可选自多孔粘土、绿坡缕石(attapulgite)粉末和类似材料,或其组合;以及
挤出助剂例如可选自表面活性剂、硬脂酸酯、植物油和类似材料,或其组合。
在一些实施方式中,流变学增塑液体可具有例如90-120cps的粘度。
在一些实施方式中,蜂窝制品可具有光滑的(即,没有撕裂、裂纹、起泡或裂缝)外部表皮和畅通无阻(即没有阻碍的或开放的)通道。
在一些实施方式中,本发明提供了蜂窝过滤器制品,其包括:
40重量%-60重量%的活性炭;
4重量%-15重量%的多孔无机粘合剂粉末;
950m2/g-1600m2/g的BET表面积;
50-2000cpsi的孔道密度;以及
0.5-0.8g/cm3的密度。
在一些实施方式中,蜂窝过滤器制品可具有例如700-1,200mg/g的碘值,这个量度是制品的优异吸附性质的指示器。
在一些实施方式中,本发明提供了一种使用本文所述的活化过滤器制品的方法,所述方法包括:
在过滤器设备中安装所述过滤器制品;以及
使流体通过安装的过滤器制品。
在一些实施方式中,流体例如可选自气体、液体或其组合。在一些实施方式中,流体可为挥发性化合物,例如芳香族苯或甲苯,获自脂肪族烃和类似化合物,它们的混合物和它们的蒸气。
在一些实施方式中,气体例如可选自天然气、工业气体、工业废气、有机溶剂蒸气、环境污染空气、来自燃烧发动机的尾气、已用催化剂处理的来自燃烧发动机的尾气,及其混合物。
在一些实施方式中,液体例如可选自液相纯化、液相回收和分离过程、天然水来源、工业流出物流和有机溶剂,及其混合物。
在一些实施方式中,本发明提供用于制备活性炭蜂窝结构的不含酚醛树脂的批料组合物。在批料组合物中不存在酚醛树脂,且以受控的量组合活性炭颗粒和合适的有机粘合剂和无机粘合剂实现成功地挤出批料组合物,以及后续的在本文所述的较低温度下将挤出的体加工成高活性、活性炭蜂窝结构。
在一些实施方式中,本发明提供通过例如下述步骤来加工本文所述的批料组合物:
混合成基本上均匀的下述物质的混合物颗粒:活性炭;多孔无机粘合剂;和第一有机粘合剂;
以足以塑化所述混合物从而是可塑性变形的量,向所述混合物添加增塑液体,所述增塑液体由粉末化的第二有机粘合剂和追加的水制备;
在环境温度例如室温下,通过合适的模头挤出所述混合物,以制备蜂窝生坯体;
在排气式烘箱中,将所得蜂窝生坯体在例如120-160℃下干燥1-24小时,例如2-10小时;以及
在氮气中,将干燥的蜂窝体在例如200-250℃下加热1-24小时,例如2-10小时,从而稳定蜂窝结构。
适用于本发明的活性炭粉末是市售的,例如购自Meadwestvaco的Nuchar SA-20(1500m2/g)和RGC(1450m2/g)活性炭,以及购自Calgon公司的BL活性炭(1250m2/g)。
可将无机粘合剂添加到批料组合物,从而增加第一有机粘合剂的粘合作用。组合物中所用的无机粘合剂可为例如多孔粘土粘合剂,例如海泡石粉末(具有通式Mg4Si6O15(OH)2·6H2O),绿坡缕石粉末(或者坡缕石(palygorskite);一种具有通式(Mg,Al)2Si4O10(OH)·4(H2O)的镁铝页硅酸盐(phyllosilicate)),和类似的无机粘合剂材料,或其组合。以添加到批料的活性炭粉末的总重量为基准计或者以不含水追加量的总批料重量为基准计,添加到批料的无机粘合剂的量可为例如5-15重量%。
粉末化第一有机粘合剂例如可选自纤维素醚和它们的衍生物。以添加到批料的活性炭粉末(例如40-60重量%)的总重量为基准计,或者以不含水追加量的批料组合物的总重量为基准计,添加到批料的第一有机粘合剂的量可为例如5-10重量%。第一有机粘合剂用作增塑剂来辅助挤出和提供润湿强度,以保持挤出的生坯形状的结构整体性。第一粘合剂例如可选自下组:甲基纤维素、羟基丁基纤维素、乙基纤维素、羟基丁基甲基纤维素、羟基乙基纤维素、羟基甲基纤维素、羟基丙基纤维素、羟基丙基甲基纤维素、羟基乙基甲基纤维素、羧基甲基纤维素钠及其混合物。优选的有机粘合剂是甲基纤维素产品,例如甲基纤维素(A4M),购自陶氏化学公司。
流变学增塑液体可通过下述来制备:取决于粘合剂,将第二有机粘合剂的粉末在60-70℃的温水中溶解1-5小时,例如2-3小时,以形成粘性液体,所述粘性液体具有可与液体酚醛树脂相比拟的粘度例如90-120cps。溶解于水中第二有机粘合剂的量可为例如5-10重量%。合适的有机粘合剂可包括例如羧基甲基纤维素钠(CMC)、聚乙烯醇(PVA)、壳聚糖和类似的材料,或其混合物。在制备壳聚糖溶液时,例如将相应量的乙酸(例如以壳聚糖重量为基准计的约5-10重量%)添加到水,以辅助溶解添加的壳聚糖粉末。
实施例
下面通过以下实施例更全面地描述本发明。下面的实施例表明根据本文所述的步骤来制备、使用和分析本文所述的活性炭蜂窝。
实施例1
根据本发明,并使用表1所示的成分,来制备活性炭蜂窝样品。排除追加量水的总批料重量是500g。通过在70℃的温水中溶解5重量%的羧基甲基纤维素钠(CMC)来制备增塑液体。所用的活性炭粉末是购自MeadWestvaco的RGC活性炭,其具有20微米的平均粒度和1450m2/g的BET表面积(SA)。通过下述来制备蜂窝:混合批料成分,通过意大利面(spaghetti)模头挤出混合的成分,和最终通过蜂窝模头(1600孔道/平方英寸)挤出意大利面。在排气式烘箱中,在140℃下干燥挤出的蜂窝。然后,例如在氮气中将干燥的蜂窝在250℃下加热2小时。使用氮气吸附和苯吸附来表征活性炭蜂窝样品的BET表面积,分别如实施例4、以及表4和表5所总结。
参考附图,在一些实施方式中,蜂窝过滤器制品可包括多个在第一端部和第二端部之间延伸的多孔通道,例如如图1所示。例如,蜂窝结构可适于用作壁流气体颗粒过滤器。根据本发明实施方式的典型蜂窝流通式(flow-through)基材制品100示于图1,该制品可包括许多通常平行的孔道110,所述孔道由交叉的孔壁140(或者称为“壁板(web)”)形成并至少部分由其限定,其从第一端部120延伸至第二端部130且随后穿透相邻的堵塞通道的壁并排出过滤器。通道110是未堵塞的,且经过通道110的流动是从第一端部120到第二端部130沿着通道笔直向下的。蜂窝制品100还包括任选的表皮150,所述表皮150绕着蜂窝结构的外部形成,且可通过挤出来形成或者在后续的加工中作为后面施加的表皮来形成。在一些实施方式中,用于基材的每一孔道壁140的壁厚度可为例如约100-约500微米,约100-约150微米和类似的壁厚,包括中间值和范围。孔道密度可为例如约50-约2000cpsi,约500-约2000cpsi,约1000-约2000cpsi,约1250-约2000cpsi,约1600-约2000孔道/平方英寸(cpsi),包括中间值和范围。在一些实施方式中,多孔蜂窝结构包括形成进入蜂窝结构的截面通常为正方形的许多平行孔道110。或者,蜂窝体结构中也可以使用其他的截面构形,包括例如矩形,圆形,椭圆形,三角形,八边形,六边形,和类似的几何形貌,或它们的组合。“蜂窝”包括形成纵向延伸的孔的孔壁结构。
图2显示根据本发明一些实施方式的示例性蜂窝壁流式过滤器200。其一般结构包括主体201,该主体201包括从第一端部202延伸至第二端部204并形成孔或孔道的交叉的多孔壁206。某些孔被称为入口孔208,某些另外的孔被称为出口孔210。在过滤器200中,一些选定的孔道包含堵塞物212。一般而言,将堵塞物设置在孔道的端部,并以某种限定的图案排列,如所示的棋盘图案。进口孔道208可以在出口端部204堵塞,出口孔道210可以在进口端部202堵塞。可使用其他堵塞图案,为增加强度,可以堵塞最外周边的所有孔(如图所示)。或者,某些孔可以不在端部堵塞。在一些实施方式中,一些孔道可以是流通的孔道,一些孔道可以堵塞,以提供所谓的部分过滤的设计。
在一些实施方式中,挤出的和活性炭蜂窝过滤器制品可具有例如约1英寸的直径和约12英寸的长度,以及约50-2000孔道/平方英寸或通道开口/平方英寸(cpsi)的蜂窝孔道密度。挤出的和活性炭蜂窝过滤器制品可具有显著不同的尺寸和几何形貌,且可使用适当地结构化的和选定的模头和挤出设备来获得不同的尺寸和几何形貌。
本发明的挤出和活化蜂窝样品可具有非常畅通无阻的和良好限定的正方形通道。在一些实施方式中,可使用已知方法和材料用合适的材料来堵塞或阻塞(未显示)紧密相邻的通道开口,以提供穿过壁(through-wall)的过滤器制品。或者,可选定通道几何形貌,例如正方形、矩形、菱形、圆形和类似图案。或者,还可选择堵塞或阻塞图案。
表1.用于在实施例1中制备的样品的批料挤出组合物
实施例2
根据本发明和使用表2所示的成分,来制备本实施例的活性炭蜂窝。排除水的总批料重量也是500g。增塑液体通过在70℃的温水中溶解5重量%的聚乙烯醇来制备。所用的活性炭粉末与实施例1的相同。以与实施例1和实施例4所述相同的方式来实施成分的配料、批料组合物的挤出、挤出的体的干燥和热处理、活性炭产品的表征和测试。
表2.用于在实施例2中制备的样品的批料挤出组合物
实施例3
根据本发明和使用表3所示的成分来制备本实施例的活性炭蜂窝。排除水的总批料重量也是500g。液体粘合剂通过在60℃的5%v/v乙酸溶液中溶解5重量%的壳聚糖来制备。所用的活性炭粉末与实施例1的相同。以与实施例1和实施例4所述相同的方式来实施成分的配料、批料组合物的挤出、挤出的体的干燥和热处理以及挤出的活性炭产品的表征和测试。
表3.用于在实施例3中制备的样品的批料挤出组合物
实施例4
蜂窝表征和评估。通过在40℃下将样品暴露于苯蒸气3小时,来测试活性炭蜂窝过滤器样品的苯吸附。此外,通过将活化蜂窝过滤器样品在100℃的热水中浸没6小时(标准测试时间是15分钟),来进行水稳定性测试。甚至在热水中延长的浸没之后,活化蜂窝过滤器样品保持其强度和结构整体性。分别在表4和表5中给出了BET SA和苯吸收数据。结果表明获得高表面积和高苯吸收。
表4.实施例1-3中样品的BET表面积,并与酚醛树脂基活性炭蜂窝比较。
表5.通过实施例1-3以及比较性酚醛树脂基活性炭蜂窝样品(暴露时间是3小时)的苯吸收。
比较例5
重复实施例1,但根据常规方法,通过共混表6中的成分(没有追加量的水),来制备基本上均匀的混合物。挤出混合和捏合的物质来获得蜂窝生坯体。在将蜂窝生坯体在140℃下干燥和固化2小时之后,在非氧化性气氛(即,N2)中在800-900℃的温度下将该体处理4小时,以制备碳化的蜂窝体。最后,取决于制品的尺寸,将碳化的蜂窝体在活化气氛(即,CO2)中在850-950℃的温度下保持8-48小时。将较大的蜂窝体干燥比较小的蜂窝体更长的时间。
表6.用于比较例5的样品的批料挤出组合物。
成分 | 重量% |
木炭 | 39.8 |
纤维素纤维(BH40) | 18 |
甲基纤维素A4M | 5.7 |
硬脂酸钠(Liga) | 1.0 |
植物油 | 2.5 |
液体酚醛树脂 | 33 |
已结合各种具体实施方式和技术对本发明进行了描述。但是,应当了解可以在本发明的范围内做出多种变化和改进。
Claims (18)
1.一种蜂窝过滤器制品,其包含:
40重量%-60重量%的活性炭;
4重量%-15重量%的多孔无机粘合剂粉末;
950m2/g-1600m2/g的BET表面积;
50-2000cpsi的孔道密度;以及
0.5-0.8g/cm3的密度。
2.如权利要求1所述的蜂窝过滤器制品,其特征在于,壁厚是100-150微米,且孔道密度是1600-2000cpsi。
3.如权利要求1或2所述的蜂窝过滤器制品,其特征在于,其具有700-1200mg/g的碘值。
4.一种制备活性炭蜂窝过滤器制品的方法,所述方法包括:
挤出批料混合物来形成挤出的蜂窝体,所述批料包含:
40重量%-60重量%的活性炭粉末;
5重量%-10重量%的第一有机粘合剂粉末;
20重量%-30重量%的流变学增塑液体,其由在水中的5重量%-10重量%的第二有机粘合剂粉末制备;
4重量%-15重量%的多孔无机粘合剂粉末;
1重量%-3重量%的挤出助剂;和
通过追加的50重量%-100重量%的水,
所述重量%基于排除了基于追加的水的批料成分的总重量;
在约120-160℃下将挤出的蜂窝体干燥1-2小时;以及
在氮气中,将干燥的蜂窝体在200-250℃下热处理2-4小时,从而制备活性炭蜂窝过滤器制品。
5.如权利要求4所述的方法,其特征在于,所述蜂窝制品具有950m2/g-1600m2/g的BET表面积。
6.如权利要求4或5所述的方法,其特征在于,使用具有50-2000cpsi孔道密度的蜂窝模头且在约15-30℃的环境温度下,来实现所述挤出。
7.如权利要求4-6中任一项所述的方法,其特征在于,所述活性炭蜂窝过滤器制品具有100-500微米的壁厚。
8.如权利要求4-7中任一项所述的方法,其特征在于:
第一有机粘合剂粉末选自下组:甲基纤维素、羟基丁基纤维素、乙基纤维素、羟基丁基甲基纤维素、羟基乙基纤维素、羟基甲基纤维素、羟基丙基纤维素、羟基丙基甲基纤维素、羟基乙基甲基纤维素、羧基甲基纤维素钠,或其混合物;
第二有机粘合剂粉末选自羧基甲基纤维素钠、聚乙烯醇、壳聚糖,或其混合物;
多孔无机粘合剂粉末选自多孔粘土、绿坡缕石粉末或其组合;以及
挤出助剂选自表面活性剂、硬脂酸酯、植物油或其组合。
9.如权利要求4-8中任一项所述的方法,其特征在于,所述流变学增塑液体具有90-120cps的粘度。
10.如权利要求4-9中任一项所述的方法,其特征在于,所述挤出的蜂窝制品和活化蜂窝制品各自具有不含皱纹的光滑的外部表皮和不含残留堵塞物的畅通无阻的通道。
11.如权利要求4-10中任一项所述的方法,其特征在于,使用具有1600-2000cpsi的孔道密度的蜂窝模头来实现所述挤出。
12.如权利要求4-11中任一项所述的方法,其特征在于,所述活性炭蜂窝过滤器制品具有100-150微米的壁厚。
13.一种使用如权利要求1所述的活化过滤器制品的方法,所述方法包括:
在过滤器设备中安装所述过滤器制品;以及
使流体通过安装的过滤器制品。
14.如权利要求13所述的方法,其特征在于,所述流体选自气体、液体或其组合。
15.如权利要求13或14所述的方法,其特征在于,所述气体选自天然气、工业气体、工业废气、有机溶剂蒸气、环境污染空气、来自燃烧发动机的尾气、已用催化剂处理的来自燃烧发动机的尾气,及其混合物。
16.如权利要求13-15中任一项所述的方法,其特征在于,所述液体选自液相纯化、液相回收和分离过程、天然水来源、工业流出物流和有机溶剂,及其混合物。
17.如权利要求13-16中任一项所述的方法,其特征在于,所述流体是挥发性有机化合物。
18.如权利要求13-17中任一项所述的方法,其特征在于,所述流体是苯蒸气。
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US5510063A (en) | 1994-04-15 | 1996-04-23 | Corning Incorporated | Method of making activated carbon honeycombs having varying adsorption capacities |
JPH08155295A (ja) * | 1994-05-31 | 1996-06-18 | Corning Inc | 炭素ボディおよびその製造方法 |
JP4322542B2 (ja) * | 2003-04-21 | 2009-09-02 | 日本碍子株式会社 | ハニカム構造体、その製造方法及び成形用口金並びに排出流体浄化システム |
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2015
- 2015-05-04 US US14/703,399 patent/US20150343418A1/en not_active Abandoned
- 2015-05-28 JP JP2016568809A patent/JP2017517391A/ja active Pending
- 2015-05-28 CN CN201580028202.XA patent/CN106457206A/zh active Pending
- 2015-05-28 EP EP15730897.4A patent/EP3148689A1/en not_active Withdrawn
- 2015-05-28 WO PCT/US2015/032771 patent/WO2015184027A1/en active Application Filing
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2019
- 2019-05-28 US US16/423,995 patent/US20190275496A1/en not_active Abandoned
- 2019-05-28 US US16/423,889 patent/US20190275495A1/en not_active Abandoned
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CN2035653U (zh) * | 1988-09-02 | 1989-04-12 | 北京市劳动保护科学研究所 | 一种蜂窝状活性炭吸附剂 |
US5356852A (en) * | 1990-12-24 | 1994-10-18 | Corning Incorporated | Activated carbon structures |
US5376609A (en) * | 1993-08-23 | 1994-12-27 | Corning Incorporated | Activated carbon bodies having bentonite and cellulose fibers |
US5488021A (en) * | 1993-12-17 | 1996-01-30 | Corning Incorporated | Activated carbon bodies having clay binder and method of making same |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108159783A (zh) * | 2018-01-12 | 2018-06-15 | 广州康瑞环保科技有限公司 | 利用自身发热烧结过滤介质的烧结方法及实施该方法的烧结装置 |
CN112074337A (zh) * | 2018-05-17 | 2020-12-11 | A.凯塞汽车系统有限公司 | 具有阻挡层的活性炭过滤器 |
US11801469B2 (en) | 2018-05-17 | 2023-10-31 | A. Kayser Automotive Systems Gmbh | Activated carbon filter having barrier layer |
CN110935425A (zh) * | 2019-12-04 | 2020-03-31 | 武汉市九合生物技术有限公司 | 一种吸附和净化非甲烷总烃的高分子复合材料、制备方法及其应用 |
CN112569901A (zh) * | 2020-12-24 | 2021-03-30 | 福建省鑫森炭业股份有限公司 | 一种低阻抗汽车碳罐用活性炭及其制备方法和应用 |
CN112933742A (zh) * | 2021-03-02 | 2021-06-11 | 全硒时代(深圳)生物科技发展有限公司 | 具有有机硒的滤芯的制造方法 |
CN117416957A (zh) * | 2023-12-19 | 2024-01-19 | 成都达奇科技股份有限公司 | 活性炭的制备方法以及活性炭 |
CN117416957B (zh) * | 2023-12-19 | 2024-04-26 | 成都达奇科技股份有限公司 | 活性炭的制备方法以及活性炭 |
Also Published As
Publication number | Publication date |
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US20190275496A1 (en) | 2019-09-12 |
US20150343418A1 (en) | 2015-12-03 |
WO2015184027A1 (en) | 2015-12-03 |
EP3148689A1 (en) | 2017-04-05 |
JP2017517391A (ja) | 2017-06-29 |
US20190275495A1 (en) | 2019-09-12 |
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