CN111699036B - 优异的碳吸附剂 - Google Patents
优异的碳吸附剂 Download PDFInfo
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- CN111699036B CN111699036B CN201980012731.9A CN201980012731A CN111699036B CN 111699036 B CN111699036 B CN 111699036B CN 201980012731 A CN201980012731 A CN 201980012731A CN 111699036 B CN111699036 B CN 111699036B
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Abstract
本发明涉及一种含有芯或不含芯的优异的碳吸附剂。在一个实施方案中,本发明的碳吸附剂采用碳吸附剂粉末和有机粘结剂,所述碳吸附剂粉末和所述有机粘结剂在凝聚步骤中与合适的溶剂组合在一起。在另一个实施方案中,本发明涉及一种芯‑壳吸附剂,所述芯‑壳吸附剂包含由碳组成的外壳以及非吸附惰性内芯。对这些凝聚体的低温处理基本上将所述粘结剂保留在最终组合物内,并允许制备高球形度的吸附剂产品。本发明的吸附剂具有优异的特性,诸如用于H2PSA工艺的较高的传质速率和CO2工作容量。
Description
相关申请
本申请要求于2019年2月14日提交的国际申请号PCT/US2019/018046的权益,该国际申请要求于2018年2月15日提交的美国临时申请序列号62/630,897的权益,该临时申请以引用方式并入本文。
技术领域
本发明涉及被制备成含有芯或不含芯的碳吸附剂及其制备方法。本发明的吸附剂的特征在于利用具有低活化温度和大于0.8的高球形度的有机粘结剂。本发明的吸附剂特别适用于H2 PSA工艺等。
背景技术
具有宽范围的孔结构和用于吸附气体的表面化学性质的活性碳可用于在变压和变温吸附方法中分离和纯化气体混合物。在气体分离方法中,活性碳通常比沸石吸附剂更优选,因为活性碳对气体的吸附强度相对适中,这有利于脱附过程。活性碳在若干商业应用中是高度有效的,例如从污染气体中去除杂质、从空气生产氮气和从蒸汽-甲烷重整器废气生产氢气。在一个示例中,活性碳用作H2PSA工艺中的吸附剂,用于去除氢气物流中的CO2和/或烃(包括CH4)。有许多现有技术的示例详细描述了该工艺,包括美国专利6,503,299。
在另一个示例中,碳分子筛在N2PSA工艺中用作吸附剂来从空气中去除氧。还有许多描述该工艺的现有技术的示例,包括仍然是重要目标的这些工艺的改进,其一个主要方式是发现和开发更有效的吸附剂。不仅在吸附选择性和容量方面,而且在提高吸附传质速率的独特方式方面,都已经实现了显著的改进。在快速传质速率的情况下,人们通常可以提高PSA/VPSA体系和方法的回收率。这在美国专利6,500,234中讨论。
增大凝聚吸附剂颗粒的传质速率的一种策略是减小吸附剂聚集体的颗粒尺寸。这通过减小吸附物行进穿过凝聚吸附剂的限速大孔所需的路径长度来增大吸附/脱附动力。然而,减小颗粒尺寸具有其局限性:无约束的吸附床中的较高压降和流化风险增大很快成为吸附工艺和系统设计的问题。此外,小颗粒尺寸凝聚体的容纳和制造代表了需要解决的其他缺点。
美国专利4,921,831描述了一种制备活性碳的方法。该方法包括将不粘结性煤粉碎到<10微米,之后进行煤粉制粒。在该过程中,可以使用添加剂来暂时增加强度,这些添加剂可包括CMC、PVA、淀粉、烃油等,可使用挤出、压缩、混合、辊压技术等来进行造粒。将所得颗粒干燥并在500℃-1000℃下在惰性气体气氛下碳化以产生足够强的活性碳凝聚体。本发明与上述方法不同,因为上述方法包括:利用碳粉末;与足量的有机粘结剂混合;以及在低温下活化,该低温足以去除包括预吸附水的组分,但不足以实现这些组合物中采用的粘结剂的完全碳化。所得珠粒具有高强度、高球形度和优异的吸附特性。与现有技术相比的明确优点是避免了以高温碳化来获得高质量的最终产品。
US2017/0247772 Al描述了一种包含芯的复合颗粒,该芯可以是石灰石、白云石或另一种矿石颗粒的聚集体,该聚集体被金属粉尘和粘结剂的涂层围绕。这种涂层的一个实施方案是氧化铁粉尘。粘结剂通常是矿物粘土诸如膨润土、蒙脱土或高岭土,并且占颗粒的约2重量%-10重量%。这些颗粒如此形成以便像任何普通矿石颗粒一样用于矿石精炼工艺中。复合颗粒的尺寸范围可以从小卵石到大尺寸岩石。本发明的颗粒可以使用辊如混凝土搅拌机的轧辊通过分批轧制法来制造。本发明用作寻找再循环和再利用金属氧化物粉尘而不必处置或启动另外的工艺措施的方法的解决方案。这与本发明形成对比,本发明将活性碳用于PSA工艺。
US2017/0203346A1描述了一种形成化学环境屏障以将污染的沉积物与环境隔离的方法。这通过用大量颗粒涂覆被污染层来实现,这些颗粒可以用作密封剂或含有消耗污染物的微生物。本发明的一个实施方案利用“AquaBlok”或“AquaGate”体系。这包括使用5mm-10mm的芯-壳颗粒,所述芯-壳颗粒具有岩石、砾石或砂类型的芯和具有至少一种反应性材料的外部密封剂层,所述反应性材料包括粘土或活性碳。AquaGate体系包括至少部分地包封在非溶胀性反应性材料内以产生多孔处理层的芯。这用作从孔隙水中去除污染物和/或降低污染物穿透的可能性的手段。AquaBlok体系提供了不可渗透的覆盖层,以将污染与表面水隔离。这与本发明不同,本发明包括在致密的芯上用活性碳外层涂覆单个颗粒,该致密的芯不是用作密封剂而是用作PSA工艺中的气体吸附剂。本文教导了用于活性碳层的粘结剂和/或添加剂的类型对气体吸附速率具有显著影响。某些添加剂可部分地阻塞吸附孔并减缓吸附速率。因为Aquablok用作密封剂,所以没有考虑影响吸附速率的添加剂。此外,在“AquaBlok”或“AquaGate”体系中使用的材料对颗粒形状没有限制。本发明使用一种形成方法,该形成方法形成明显更具球形的颗粒形状,以产生具有低压降和优异气流分布特性的吸附床。
US2013/0196061A1描述了用至少部分地包封芯的可水合材料层涂覆单个颗粒的方法。该实施方案利用如先前现有技术中提及的“AquaBlok”颗粒体系。此外,纤维增强材料用于至少部分地包封所述芯。纤维材料可以单独成层或与可水合材料预混合。添加纤维作为增强材料以向颗粒提供额外的强度。可水合材料通常由粘土组成,粘土在水合时膨胀并形成屏障基质。该复合颗粒与本发明的复合颗粒的不同之处在于,本发明的复合材料不含任何纤维状增强材料。该涂层由活性碳和粘结剂组成,并且不是制备来用作密封剂,而是被设计和调节来用作PSA工艺中的气体吸附剂。
EP 1,080,771描述了一种芯-壳复合吸附剂,该芯-壳复合吸附剂具有包括无孔且非吸附材料的内芯以及包含吸附材料的至少一个外层。此类复合珠粒可用于在不减小珠粒的颗粒尺寸的情况下改善吸附工艺中的传质。EP1,080,771中的公开内容仅教导了优选的芯类型和吸附剂壳类型。未公开其他组分,包括作为本发明复合材料的特征的一种或多种粘结剂,以及保留或基本上保留作为最终组合物的一部分的一种或多种粘结剂的关键低温加工。
美国专利5,236,688描述了一种在流化床中煅烧和活化球形沥青珠粒的方法。在上段中,在600℃-800℃之间煅烧珠粒,然后将珠粒排出到下段,在下段中在800℃-1200℃之间活化珠粒。本发明着重于对煅烧方法的改进,以便提高收率并降低能耗。阐述了一种形成沥青珠粒的方法,该方法包括熔融模塑珠粒,方式是首先挤出沥青,加热破碎的挤出物到它们的软化点,然后将它们投入水中形成球体。本发明的复合吸附剂由于前述原因而不同,因为碳-粘结剂凝聚体在低温下活化,该温度仅足以去除包括预吸附水的组分。在不进行高温碳化的情况下,可以制备具有优异吸附特性的高强度、高球形度的碳吸附剂。
授予Gerds等人的美国专利8,814,985公开了具有多孔非吸附芯和多孔吸附壳的芯-壳复合吸附剂珠粒的制备,声称多孔芯能够以甚至更少的无机粘结剂并因此更高的总吸附容量来提高珠粒强度。优选地通过将未烧结的芯和吸附剂层一起煅烧,并添加无机粘结剂(高岭土)以及有机形成助剂(例如聚乙烯醇、甘油和聚硅氧烷等)来制造珠粒。从Gerds等人的公开内容中,未教导被制备含有有机粘结剂的碳吸附剂,以及使用低温热处理来保留或基本上保留作为产品组合物的一部分的粘结剂。
本发明涉及一种具有高球形度的独特碳吸附剂,该碳吸附剂表现出优异的吸附特性和物理强度。本发明的碳吸附剂包含吸附剂碳和有机粘结剂,其中采用低温处理以将粘结剂保留或基本上保留在最终组合物内。在一个实施方案中,将无孔芯添加到组合物中以形成芯-壳碳吸附剂。在芯-壳实施方案中,使用具有高体积热容量的无孔芯来生成具有快速动力学特性和热管理特性的碳吸附剂产品。本领域的技术人员将认识到快速吸附动力学特性能够实现过程强化。热管理方面潜在地能够抑制吸附床中不利的热梯度,这继而可以使PSA工艺中的吸附剂工作容量提高。
发明内容
本发明提供了用于吸附分离工艺的优异的凝聚吸附剂组合物,所述吸附分离工艺包括循环气体分离工艺诸如H2 PSA。本发明涉及一种优异的碳吸附剂,该碳吸附剂可以使用本领域已知的商业制造方法制备,具有良好的物理强度,以及较高的传质速率和热容量。
在另一个实施方案中,吸附剂以芯-壳排列设置,其中惰性芯被包含碳吸附剂的壳围绕。更具体地,芯-壳材料的特征在于:1)非吸附惰性芯材料,例如铝土矿氧化铝,其孔隙率≤10%且体积热容量≥1J/cc-°K;2)该芯占据的总体积为10%-90%,和3)其中吸附剂壳包含活性碳和粘结剂,并且其中平均产品尺寸在0.5mm至5mm的范围内且产品球形度大于0.8。
活性碳可来源于多种来源。任何含碳物质都可以用作活性碳的原材料。所用的原材料取决于获得材料的难度、所需的量、价格、与气体或化学品的反应性,以及产品质量的适当性。通过在活化气体的存在下加热到700℃以上以产生多孔材料来实现碳原材料的活化。诸如木炭、椰子壳和煤的大多数活性碳来源以颗粒形式活化,随后粉碎到<0.1mm成为粉末形式,其准备用于与一种或多种粘结剂凝聚成为本发明的高球形度碳吸附剂颗粒。
粘结剂用于确保活性碳对其自身的粘附,并且在使用芯的情况下确保对芯的粘附。一种或多种粘结剂可以包括任何增塑有机粘结剂材料。这些可以包括粘结剂,诸如任何多糖,如葡聚糖、糊精、玉米淀粉、纤维素醚等,或任何有机聚合物。在一个实施方案中,本发明的吸附剂是芯-壳碳吸附剂,其中芯选自具有高密度(低孔隙率)和优选具有高热容量的材料。低孔隙率被认为是重要的,以便使芯-壳颗粒中的非选择性气体吸附最小化。理想地,当通过Hg孔隙率测定技术(参见“Analytical Methods in Fine Particle Technology”第4章,Paul A.Webb和Clyde Orr,ISBN 0-9656783-0X(1997))测量时,芯的孔隙率为10%或更小。需要具有高热容量(例如至少1J/cc-K)的芯,以便控制已知在诸如H2 PSA的工艺过程中存在于吸附床内的热梯度。
附图说明
图1示出本发明的珠粒制备顺序的示意图。
具体实施方式
本发明涉及一种含有芯或不含芯的优异的碳吸附剂。在一个实施方案中,本发明的碳吸附剂采用碳吸附剂粉末和有机粘结剂,所述碳吸附剂粉末和所述有机粘结剂在凝聚步骤中与合适的溶剂组合在一起。在另一个实施方案中,本发明涉及一种芯-壳吸附剂,该芯-壳吸附剂包含由碳组成的外壳以及非吸附惰性内芯。对凝聚体进行低温处理,该低温处理基本上将粘结剂保留在最终组合物内,并允许制备高球形度的吸附剂产品。所生产的吸附剂具有优异的特性,诸如用于H2PSA工艺的较高的传质速率和CO2工作容量。较高传质速率的益处已经得到充分证明,而在VSA/VPSA/PSA体系中较高热容量的益处也通过引入实芯而被独立地证明。本发明通过识别真实环境中的优选性能而建立在这些观察之上。
对于芯-壳吸附剂,优选的芯体积比范围取决于具体的应用。当用于体相气体分离工艺时,芯体积比的优选范围为约10%-30%。体相气体通常被定义为含有大于约1体积%的待吸附气体。在这种情况下,优选较高百分比的碳壳以使工作气体容量最大化。在纯化过程中,优选的芯体积比范围为约60%至90%。当从物流中仅去除少量气体时,吸附速率变得更重要,并且较薄的壳将导致较高的吸附速率。该廉价的芯-壳吸附剂显著改善PSA性能,同时表现出良好的抗磨性和低商业制造成本。
芯体积比通过芯的体积除以最终芯-壳凝聚体的体积来测量。两者均使用球体积公式(4/3)πr3。使用通过筛网测定的平均颗粒尺寸来确定半径。约5%-20%的芯体积比对应于约37%-58%的直径比。
在本领域中已知有许多吸附剂组合物和制造方法用于空气分离工艺和/或烃处理。有许多用于吸附剂凝聚的方法。这些方法包括挤出、压缩、混合、轧制、盘式造粒等。先进吸附剂的开发和商业化中所面临的挑战是平衡物理特性和吸附特性。具有较高速率的材料趋于具有减小的物理强度,如通过压碎强度和磨耗所测量的。
本发明的碳吸附剂采用碳吸附剂粉末和有机粘结剂,当在凝聚步骤期间与适当的溶剂组合在一起时,所述碳吸附剂粉末和所述有机粘结剂允许制备具有高球形度的吸附剂产品。一种使颗粒凝聚以获得具有高压碎强度和低磨耗的最终产品的方法是使用分层方法,其中依次设置粘结剂层接碳吸附剂的交替层。在芯-壳碳吸附剂的一个实施方案中,在沉积碳吸附剂层之前,可以用粘结剂涂覆芯,并且继续该过程以实现所需的芯-壳比。可以使用相同的一般方法来形成不含芯的碳吸附剂。
在一个实施方案中,本发明的碳吸附剂包含:
·75重量%-99重量%的至少一种碳吸附剂。
·1重量%-25重量%,在另一实施方案中2重量%-12重量%以及在另一实施方案中3重量%-7重量%的至少一种粘结剂,其中吸附剂的特征在于球形度>0.8以及在200℃至500℃之间的活化温度下大于或等于2重量%至最多约15重量%的LOI。
吸附剂的特征还在于产品颗粒尺寸为约0.5mm-5.0mm,优选与用于常规VSA/VPSA/PSA工艺的相同,并且碳吸附剂产品的磨耗损失小于或等于约5%。
在另一个实施方案中,本发明的碳吸附剂是芯-壳材料,该芯-壳材料包含:
·吸附剂壳,该吸附剂壳包含75重量%-99重量%的至少一种碳吸附剂和1重量%-25重量%,在另一实施方案中2重量%-12重量%以及在另一实施方案中3重量%-7重量%的至少一种粘结剂。
·惰性芯,该惰性芯具有极低的孔隙率和比氧化铝大的体积热容量,在一个实施方案中孔隙率≤10%,在另一个实施方案中≤5%;并且体积热容量≥1J/cc-K,在另一个实施方案中≥2.5J/cc K)
·在珠粒中10%-90%体积比的芯,在另一个实施方案中,当用于体相分离时在珠粒中10%-30%体积比的芯,以及当用于纯化分离时在珠粒中60%-90%体积比的芯,用于性能、容量和强度之间的关键平衡。
·0.5mm-5.0mm的产品颗粒尺寸,优选与用于常规VSA/VPSA/PSA工艺的相同。
·小于或等于5重量%的芯-壳碳吸附剂产品的磨耗损失。
原则上,适用的碳吸附剂组合物可以是任何碳吸附剂材料,包括称为活性碳的那些,包括椰子壳、木炭、煤、木屑衍生材料以及它们的混合物等。活性碳具有超过2,500种商业产品应用,并且最常用于从水和工艺气相物流中去除各种溶解的污染物。一般来讲,活性碳由碳化原材料(椰子壳、木炭、煤等)和气体(蒸气、二氧化碳、空气和燃烧气体)产生,它们在高于700℃的高温下反应产生具有直径为约10埃至200埃的微孔的材料。活性碳的另一个有吸引力的特征是它们的约500m2/g-2500m2/g的大表面积,这使得各种底物能够被吸附在表面上。在我们的示例中,使用椰子壳活性碳粉末。粉末状活性碳,诸如在我们的实施方案中所使用的,通常通过将较大的活性碳颗粒研磨小至微米级粉末来制备。其他类别的碳材料,诸如碳分子筛(CMS),可以类似地被磨成粉并与本文所述的制造方法一起使用,以由这些其他种类的碳起始材料制备碳吸附剂。CMS产物经常用于分离空气以生产氮气产品。在制备或获得粉末形式的一种或多种碳起始材料之后,其中粉末颗粒尺寸有利地≤50μm,优选≤25μm,最优选≤10μm,将其与一种或多种粘结剂组合在一起。
就粘结剂选择而言,重要的是使用这样的粘结剂体系,其有效地将活性碳颗粒粘结在一起,同时不会由于部分或完全堵塞一部分吸附位点而降低活性碳的吸附容量或吸附动力学特性。因此,粘结剂优选地选自包括多糖(葡聚糖、糊精、玉米淀粉、纤维素醚等)、有机聚合物以及它们的混合物的组。本发明的碳吸附剂中的粘结剂的组成范围已基于提供所需的压碎强度和/或抗磨性以供使用,而在同时仍实现具有所需吸附容量和吸附动力学特性的产品的组成范围而确定。
本发明的吸附剂中的粘结剂的量通常为约1重量%至25重量%,在另一个实施方案中为约2重量%至12重量%;在另一个实施方案中为约3重量%至约7重量%。当然,使用尽可能少的粘结剂是有利的,因为这被认为是必要的。只要达到足够的强度和磨耗性能,使用较少的粘结剂将导致较高的吸附容量和潜在的较高的吸附动力学特性。如在实施方案中可以看出,不同的粘结剂将导致不同的吸附和强度特性,并且必须根据应用的要求来调节所使用的量和类型。
本发明的特别有效的用于碳吸附剂的凝聚方法是在凝聚之前将所需粘结剂的一部分与被磨成粉的碳一起共混,并在凝聚期间将粘结剂的剩余部分添加该混合物中。二次粘结剂添加的这一阶段可以通过将粘结剂溶解或分散在合适的溶剂如水中来进行。通过添加预混的碳吸附剂+粘结剂的“层”,然后将其用溶解和/或分散在合适溶剂中的仅粘结剂的“层”喷涂,可以层状方式使碳吸附剂的颗粒生长至目标颗粒尺寸。这种逐层生长一直持续到达到目标颗粒尺寸。我们已经发现,这种方法在干燥后产生含有粘结剂的最终产品,所述产品满足压碎强度和/或磨耗要求,并且同时产生具有高容量和快速吸附动力学特性的最终吸附剂产品。这种凝聚方法适用于本发明的含有芯或不含芯的碳吸附剂。用于二次粘结剂添加和逐层生长的合适粘结剂的示例是溶解在水中的葡萄糖聚合物(例如葡聚糖和聚簇糊精),该溶解在水中的葡萄糖聚合物由于其“粘性”而被证明是高度有效的,因为这种粘性有助于碳吸附剂粉末粘附到其自身和/或芯,这实现了可控的颗粒生长。
对于本发明的芯-壳实施方案,将孔隙率相当低的惰性芯添加到组合物中,并且碳和粘结剂此时形成壳。本发明的惰性芯(其中术语惰性意味着芯的反应性和吸附性能可忽略不计)的通过Hg孔隙率测定法测量的总孔隙率小于或等于约10%,在另一个实施方案中小于或等于约5%,在另一个实施方案中小于或等于约2%。孔隙率被定义为非实心或孔体积分数,即孔体积/总体积。由于孔隙率是体积比,因此它是无量纲的,并且通常以分数或百分比报告。优选的低孔隙率芯材料包括但不限于致密陶瓷、砂、铝土矿、堇青石、方沸石、赤铁矿、磁铁矿、花岗石、大理石、白云灰岩和页岩等。在一个实施方案中,优选的芯是铝土矿。
本发明的复合材料的惰性芯也基于其体积热容量进行选择,以便控制可存在于吸附剂床中的热梯度。不受理论的束缚,据信对吸附过程的性能改进,更具体地对VSA/VPSA/PSA性能的性能改进,可通过选择热容量值≥1J/cc-°K且优选≥2.5J/cc-°K的这种惰性非多孔的芯来实现。由于热容量值与均质常规吸附剂中的典型热容量值相比更高,目前的新型芯-壳碳吸附剂具有管理可分别在吸附和脱附时产生的不利温度梯度的能力。与现有技术教导相比,我们认识到,如果碳芯-壳吸附剂的应用是体相分离或纯化,则必须以不同方式调节芯-壳比。本文中的体相分离被定义为其中进料含有至少一种以>1体积%的浓度存在于进料中的待吸附杂质的分离。纯化在本文中被定义为至少一种待吸附杂质以≤1体积%的浓度存在于进料中的情况。如果预期的分离是体相分离,则芯-壳体积比优选在10%-30%的范围内。如果预期的分离是纯化,则芯-壳体积比优选在60%-90%的范围内。对于预期存在热梯度的应用,希望使用尽可能高的体积热容量材料,同时保持优选的芯-壳体积比,如上所述,这取决于分离是体相分离还是纯化。材料的热容量应该在操作使用条件下使用标准参考来确定。国家标准研究院(National Institute of Standards)是一个这种参考的示例。如果芯材料是复合材料,则应该根据通常接受的实践来计算热容量。用于操作用途的典型温度是200°K至500°K。
此外,合适的芯不应具有异常的密度。密度被定义为每体积物质的质量,通常表示为g/cm3或kg/m3。随着密度增加,材料制造期间的加工成本,以及运输最终产品的成本、将吸附剂装到容器中的装载成本和容器结构成本增加。优选的芯将具有的密度小于约6g/cc;在另一个实施方案中小于约5g/cc。
表1.材料体积热容量(J/cc-°K)
表1是从国家标准研究院获得的数据样本。
本发明的碳吸附剂的适用于含有芯和不含芯的碳吸附剂的关键特征是低温干燥步骤,进行该步骤是为了调节材料以供使用。与现有技术的组合物和制造方法不同,干燥步骤在≤250℃且优选≤200℃的低温下进行。在这些低温下,一种或多种粘结剂基本上作为产品组合物的一部分而被保留,并且基本上去除了残余溶剂,包括任何水。在现有技术的组合物中,如果使用粘结剂,则使用通常>700℃的高温来分解粘结剂,并将它们转化为新的含碳材料。该低温干燥步骤最好在惰性吹扫气体(例如氮气或氩气或其混合物)或真空下进行。原则上,可以使用实现干燥材料和基本上保留粘结剂作为最终产品组合物的一部分的任务的任何吹扫气体或方法。建立粘结剂保留的方法是烧失量测试方法(LOI)。该方法在实施例部分中详细描述。与现有技术的组合物不同,本发明的吸附剂的特征在于高LOI值,这是由于在最终组合物中保留了粘结剂。本发明碳吸附剂的LOI通常为约1重量%-15重量%,在另一实施方案中为约2重量%-10重量%,并且在又一实施方案中为约2重量%-5重量%。
复合吸附剂的优选形式是球形度为至少0.8的球形颗粒,如包括颗粒图像分析方法的合适方法所测量的。通常,在颗粒图像分析方法中,分析每个样品的多个颗粒(例如>100个颗粒),并计算作为所有颗粒的平均值的球形度。尽管优选球形度≥0.8的颗粒,这些颗粒包括珠粒,但也可使用其他形式如粒料、挤出物等。就优选的颗粒尺寸而言,那些在VSA/VPSA/PSA体系中提供可接受的压降的是可接受的,例如,对于很多设计,在4×30US目尺寸范围内的颗粒是典型的。
本文提供的具体实施例公开了具有不同粘结剂并且在芯-壳组合物中的本发明的碳吸附剂。这些实施例表明所述产品具有优异的强度和吸附特性。
对于下面描述的实施例和比较例(其中公开了碳吸附剂芯-壳组合物),采用下面的一般化制备方法(参见图1)。
步骤1:测量并在合适的搅拌器中混合碳、粘结剂和水。一般来讲,任何具有足够高剪切力的搅拌器如犁式搅拌器或Hobart搅拌器都是足够的。优选在添加粘结剂之前将水添加到活性碳中。用水填充活性碳孔可减少孔进入粘结剂,从而降低部分孔堵塞的概率。在混合期间添加的水量应足以完全使粉末饱和而不形成块状物。
步骤2:将芯颗粒预筛至所需颗粒尺寸,将合适量的此类芯装载到作为珠粒形成机的旋转轮中。当轮以稳定的速度旋转时,喷涂聚簇糊精溶液或类似的替代物,同时交替添加上述粉末混合物。通过继续这种操作使珠粒生长,直到形成所需的珠粒尺寸。在该实施例中,铝土矿芯尺寸为1.0mm,最终凝聚体尺寸为1.4mm-2.36mm。这导致芯/凝聚体体积比为约8%至36%。根据应用,可能需要不同的体积比。需要较高吸附速率的应用将需要较高的比率,从而产生较薄的壳。需要较高工作气体吸附容量的应用将使用较低的体积比。对于本领域的技术人员来说,本发明所示的芯-壳实施例可以产生任何范围的体积比。珠粒中芯的体积百分比可以用估计的芯的平均颗粒尺寸相对于最终产品计算。
步骤3:在氮气流中将珠粒干燥至200℃并持续约4小时。
对于本文公开的不是芯-壳型的碳吸附剂组合物,可使用图1中所示的一般化制造方法。制备这些非芯-壳吸附剂的主要变化是在上述步骤2中,其中不使用芯,而是仅使用碳、粘结剂和水组分使珠粒生长至目标尺寸。
实施例1-活性椰子碳结合葡聚糖粘结剂18030-01N(6%粘结剂,1.0mm铝土矿芯)
将470克活性椰子碳粉末(Caigon)置于Hobart搅拌器中。然后,在搅拌器搅拌下,以10ml/min的速率泵入120克水。在添加结束时,继续混合,同时历经5分钟的时段逐渐添加30.0克葡聚糖(分子量:500,000)。在添加结束时,继续混合15分钟。将在下文中标记为“制剂”的混合粉末产品移出并暂时置于容器中。将300克16×20目铝土矿支撑剂(获自Agsco)置于12”直径的旋转盘制粒机中,并在其中以30rpm的速度搅拌。缓慢喷入5%葡聚糖溶液,同时逐渐添加制剂。将进入8×14筛目尺寸的珠粒作为产品移出。总共将312.0克椰子碳粉末、葡聚糖、水粉末混合物和124.0克5%簇葡聚糖溶液添加到旋转盘中。在烘箱干燥之前,将8×14目产品珠粒空气干燥过夜。浅托盘干燥方法使用通用信号公司(General SignalCompany)Blue-M电烘箱,其配备有干燥氮气吹扫装置。将吸附剂铺开在不锈钢网状托盘中以提供薄层。在干燥期间,将200SCFH的干燥空气送入烘箱。温度设定为90℃,然后停留360分钟。然后历经360分钟时段的过程将温度逐渐升高至200℃(近似升温速率=0.31℃/min),并在热装瓶之前在那里保持4小时。
实施例2-活性椰子碳结合microthene粘结剂18030-02N(12%粘结剂,1.0mm铝土矿芯)
将440克活性椰子碳粉末(Calgon)放入Hobart搅拌器中。然后,在搅拌器搅拌下,以10ml/min的速率泵入120克水。在添加结束时,继续混合,同时历经5分钟的时段逐渐添加60.0克Microthene FN51000。在添加结束时,继续混合15分钟。将在下文中标记为“制剂”的混合粉末产品移出并暂时置于容器中。将300克16×20目铝土矿支撑剂(获自Agsco)置于12”直径的旋转盘制粒机中,并在其中以30rpm的速度搅拌。缓慢喷入5%葡聚糖溶液,同时逐渐添加制剂。将进入8×14筛目尺寸的珠粒作为产品移出。总共将258.0克椰子碳、葡聚糖、水粉末混合物和99.0克5%簇葡聚糖溶液添加到旋转盘中。在烘箱干燥之前,将8×14目产品珠粒空气干燥过夜。浅托盘干燥方法使用通用信号公司(General Signal Company)Blue-M电烘箱,其配备有干燥氮气吹扫装置。将吸附剂铺开在不锈钢网状托盘中以提供薄层。在干燥期间,将200SCFH的干燥空气送入烘箱。温度设定为90℃,然后停留360分钟。然后历经360分钟时段的过程将温度逐渐升高至200℃(近似升温速率=0.31℃/min),并在热装瓶之前在那里保持4小时。
实施例3-活性椰子碳结合甲基纤维素粘结剂SRS 2086.2(7%粘结剂,1.0mm铝土矿芯)
将20.0磅活性椰子碳粉末(Calgon)置于MLH LS-50犁式搅拌器中。然后,在搅拌器以250rpm搅拌下,以100ml/min的速率泵入5.6磅水。在添加结束时,继续混合,同时历经15分钟的时段逐渐添加683.4克甲基纤维素(8000cps)。在添加结束时,继续犁式混合另外15分钟。将在下文中标记为“制剂”的犁式混合粉末产品移出并暂时置于筒中。将20磅从Agsco获得的16×20目铝土矿支撑剂置于内部工作容积为~75L的倾斜转筒搅拌器中,并在其中以24rpm的速度搅拌。历经8小时的时段,缓慢喷入7%的聚簇糊精溶液,同时逐渐添加制剂。将进入8×14筛目尺寸的珠粒作为产品移出。每去除1000g珠粒,就将400g(16×20)铝土矿芯添加到转筒搅拌器中。将总共155.5磅椰子碳、甲基纤维素和水粉末混合物,以及57.5磅7%簇糊精溶液添加到转筒中。在烘箱干燥之前,将8×14目产品珠粒空气干燥过夜。浅托盘干燥方法使用通用信号公司(General Signal Company)Blue-M电烘箱,其配备有干燥氮气吹扫装置。将吸附剂铺开在不锈钢网状托盘中以提供薄层。在干燥期间,将200SCFH的干燥氮气送入烘箱。温度设定为90℃,然后停留360分钟。然后历经360分钟时段的过程将温度逐渐升高至200℃(近似升温速率=0.31℃/min),并在热装瓶之前在那里保持4小时。
在这些实施例中,在芯-壳吸附剂的壳中使用3种不同的粘结剂,其中铝土矿构成芯。自始至终使用相同的椰子壳活性碳,并使用旋转轮完成所有珠粒形成。在实施例1、实施例2和实施例3中,所用的粘结剂分别为6%葡聚糖、12%microthene和7%甲基纤维素。通过不同的技术表征实施例1-3的最终碳吸附剂产品,并将结果汇总在表2中。如表2中的数据所示,使用不同的粘结剂可以导致极其不同的吸附和物理特性。最优选使用将使物理性能最大化而不引起吸附速率降低(吸附速率降低很可能是由于碳孔隙被部分堵塞)的粘结剂。
表2:使用不同粘结剂制备的芯-壳碳吸附剂的特性
珠粒尺寸表示芯-壳吸附剂产品的平均颗粒尺寸。通过标准筛选分析方法,使用100g煅烧材料,在配备有8"直径美国标准网筛的RX-29型筛网振荡器中通过15分钟搅拌来测定平均颗粒尺寸。对于这些实施例,颗粒都落入美国筛目尺寸10和12(10×12目)之间。使用与产品珠粒相同的方法来测量铝土矿芯尺寸。
使用Micromeritics AutoPore IV仪器来执行用于确定颗粒内的空隙体积和吸附剂孔隙率的汞(Hg)孔隙率测量。每次测量使用约1g的样品。将接触角固定在135°,并在0.5psia至61,000psia的压力范围内记录侵入数据和挤出数据。对汞的接触角以及关于孔隙率测量的其他相关信息可见于“Analytical Methods in Fine Particle Technology”第4章,Paul A.Webb和Clyde Orr,ISBN 0-9656783-0X(1997)。
使用Dr.Schleuniger Pharmatron Tablet Tester 8M进行压碎强度测量。在测试之前将珠粒活化,之后测试40个珠粒并将最小压碎强度进行平均。
使用McBain天平测量CO2吸附速率。McBain天平使用附接到石英玻璃弹簧上的样品盘或桶的线性位移来测量由特定样品吸附的气体量。石英玻璃弹簧被包含在垂直玻璃管内,该垂直玻璃管提供受控的大气空间,可在受控的温度和压力条件下向该大气空间中引入试验气体。在本文所述的实验中,每个McBain测量使用~1克样品。用于单个样品测量的一般规程如下:
1.使McBain装置处于室压,使用测高仪或类似合适的设备记录“空桶读数”(E)
2.向样品桶中装入~1克样品,将玻璃管固定在样品桶周围并将石英玻璃弹簧置于适当位置,并记录“活化前读数”。
3.抽空围绕样品桶和石英玻璃弹簧的玻璃管内的样品空间。
4.在真空度已稳定之后,以0.8℃/分钟的速率将各管加热至200℃,并将样品在该温度下保持至少6小时,同时继续抽空样品空间至样品彻底脱气。
5.将样品管冷却至室温,并使用测高仪记录“活化读数”(A)。
6.对于二氧化碳测量,将各管暴露于10托压力下的二氧化碳,并在暴露1分钟和60分钟后使用测高仪记录“吸附读数”(F)。
在进行二氧化碳测量之后,可以使用公式1来计算吸附容量:
气体吸附容量,质量-%=100(A-F)/(E-A) (1)
其中:A=活化读数,mm
E=空桶读数,mm
F=吸附读数,mm
100=转换系数,质量/质量转换成质量-%
表2中的吸附速率数据被表示为相同样品暴露1分钟后吸附的CO2的百分比(%)与暴露60分钟后吸附CO2的百分比(%)的比率。该比率可在0和1之间变化,其中比率为1表示在1分钟暴露时间之前达到CO2吸附平衡。
球形度是物体的形状接近数学上完美的球体的形状的程度的量度。球形度在数学上定义为Y=As/Ap,其中Y是球形度,Ap是测试颗粒P的表面积,As是与P具有相同体积的球体S的表面积。例如,使用Future Labs LLC,Madison,MS对实施例3进行球形度试验,测得球形度为0.932。
烧失量(LOI)值表示在200℃至500℃在氮气下加热碳吸附剂产品样品并在200℃下在原位预处理步骤以去除水和其他弱保持组分之后将样品在500℃下保持一小时的重量损失。200℃至500℃的LOI被表示为相对于200℃下一小时后的重量百分比。记录LOI值的便利方法使用热重量分析,热重量分析使得能够在高温下记录重量变化。所开发的方法使用高纯度氮气作为平衡吹扫气体(通常使用的)和进行样品吹扫。本文提供的结果记录在来自TA Instruments的TGA55热重量分析系统上。对于所有实验,使用5cc/分钟的平衡吹扫,并且将样品正上方的气体设定为95cc/分钟。所有研究均使用铂盘,200℃预处理后的样品尺寸为80mg至120mg。
TGA方法包括原位预处理步骤以及之后的LOI阶段。通过在氮气吹扫下以10℃/分钟将样品加热至200℃并将样品在200℃下恒温保持60分钟来进行样品预处理。该预处理结束时的样品重量被定义为活化样品重量(ASW)。对于LOI阶段,将样品以10℃/分钟加热至500℃,然后在冷却至环境温度之前,将温度保持在500℃达60分钟。在500℃下60分钟后的重量被称为较高温度下的重量(WHT)。本文所用的200℃至500℃的LOI对应于活化样品重量与较高温度下的重量之间的重量差除以活化样品重量,然后将结果乘以100以将该值转换为百分比。在数字上,这对应于:
LOI={(WHT-ASW)/ASW}×100
选择该温度范围以便仅测量从粘结剂释放的挥发物。200℃的起始温度足够高到去除任何残余水,但足够低以致本发明提出的粘结剂尚未开始分解过程,并且到500℃时应完全分解。该方法适用于含有芯或不含芯的碳吸附剂。然而,对于用于纯化气体分离中的芯-壳产品(其中芯-壳吸附剂的芯体积比在约60%至90%的范围内),必须将壳与芯分离,并且仅测量壳部分的LOI。这可以通过应用温和的研磨技术或类似的此类方法来实现。
当比较物理性能和吸附性能时,重要的是对于每个实施例使用类似尺寸的芯和最终的芯-壳产品尺寸。具体地,当比较不同尺寸的颗粒时,压碎强度和吸附速率可以显著变化,压碎强度随着尺寸而增加,而吸附速率可能由于增加的扩散路径长度而降低。孔隙率和颗粒密度的显著差异(可根据形成方法而变化)也可影响物理特性和吸附特性。较高孔隙率的材料趋于具有较高的强度和较低的速率。实施例1和实施例2具有类似的尺寸和孔隙率,并且性能方面的任何差异都可归因于粘结剂类型的变化。
Claims (16)
1.一种用于气体分离的芯-壳碳吸附剂,所述芯-壳碳吸附剂包含吸附剂壳和10体积%-90体积%的惰性芯,所述惰性芯具有小于或等于10%的孔隙率,其中所述吸附剂壳包含75重量%-99重量%的至少一种碳吸附剂和1重量%-25重量%的至少一种粘结剂,其中所述吸附剂具有0.5mm至5mm的颗粒尺寸以及>0.8的球形度,其中所述粘结剂是多糖,且其中所述吸附剂具有在200℃至500℃之间的活化温度下在2重量%至15重量%范围内的烧失量。
2.根据权利要求1所述的芯-壳吸附剂,其中所述惰性芯选自致密陶瓷、砂、铝土矿、堇青石、方沸石、赤铁矿、磁铁矿、花岗石、大理石、白云灰岩、页岩以及它们的组合。
3.根据权利要求1所述的芯-壳吸附剂,其中所述芯具有0%至5%的孔隙率。
4.根据权利要求1所述的芯-壳吸附剂,其中所述碳为来源于煤、木炭、木材、椰子壳、聚合物、沥青以及它们的混合物的活性碳。
5.根据权利要求1所述的芯-壳吸附剂,其中所述碳为碳分子筛。
6.根据权利要求1所述的芯-壳吸附剂,其中吸附剂壳包含2重量%至12重量%的粘结剂。
7.根据权利要求1所述的芯-壳吸附剂,其中吸附剂壳包含3重量%至7重量%的粘结剂。
8.根据权利要求1所述的芯-壳吸附剂,其中所述吸附剂的磨耗损失小于或等于5重量%。
9.根据权利要求1所述的芯-壳吸附剂,其中在10托和室温下暴露于CO2时,1分钟时的CO2的吸附是1小时处的吸附的至少50%。
10.根据权利要求1所述的芯-壳吸附剂,其中压碎强度>1磅/力。
11.根据权利要求1所述的芯-壳吸附剂,其中对于在体相气体分离中的使用,所述芯-壳吸附剂的芯体积比在10%至30%的范围内。
12.根据权利要求11所述的芯-壳吸附剂,其中惰性芯具有高于1J/cc-K的体积热容量。
13.根据权利要求1所述的芯-壳吸附剂,其中所述吸附剂的壳部分具有在200℃至500℃之间的活化温度下在2重量%至15重量%范围内的烧失量。
14.一种用于从气体混合物中分离至少两种具有不同吸附特性的气体组分的循环体相气体分离方法,所述方法包括将所述气体混合物送入容纳根据权利要求1所述的吸附剂的吸附容器中,其中所述吸附剂能够优先吸附所述气体混合物中的一种组分,并将所述一种组分与通过所述吸附容器的未吸附组分分离而作为回收产物。
15.根据权利要求14所述的方法,其中所述分离通过真空变动吸附、真空变压吸附或变压吸附进行。
16.根据权利要求14所述的方法,其中所述吸附剂还去除氮氧化物、烃或两者。
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RU2745299C1 (ru) * | 2018-02-15 | 2021-03-23 | Праксайр Текнолоджи, Инк. | Высококачественные композитные адсорбенты с компонентом типа "ядро в оболочке" для систем vsa/vpsa/psa |
EP3708239A1 (de) * | 2019-03-13 | 2020-09-16 | Linde GmbH | Verfahren und anordnung zur bearbeitung eines gasgemischs |
CN112717555A (zh) * | 2020-12-10 | 2021-04-30 | 安徽鸿狮环保科技有限公司 | 一种水处理用活性炭滤芯生产工艺 |
CN112705168B (zh) * | 2021-01-18 | 2022-06-21 | 太原理工大学 | 超微孔mof吸附剂材料的成型方法 |
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- 2019-02-14 CN CN201980011598.5A patent/CN111683744B/zh active Active
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US20210031171A1 (en) | 2021-02-04 |
SA520412612B1 (ar) | 2024-01-15 |
CN111683744A (zh) | 2020-09-18 |
WO2019161082A1 (en) | 2019-08-22 |
BR112020015541B1 (pt) | 2023-11-14 |
EP3752283A1 (en) | 2020-12-23 |
RU2762278C1 (ru) | 2021-12-17 |
EP3752283B1 (en) | 2022-04-27 |
DK3752283T3 (da) | 2022-05-23 |
MY195846A (en) | 2023-02-23 |
SA520412623B1 (ar) | 2024-01-10 |
RU2745299C1 (ru) | 2021-03-23 |
CN111699036A (zh) | 2020-09-22 |
PL3752283T3 (pl) | 2022-08-29 |
CN111683744B (zh) | 2023-08-15 |
WO2019161077A1 (en) | 2019-08-22 |
BR112020015541A2 (pt) | 2021-02-02 |
US20200368724A1 (en) | 2020-11-26 |
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