CN104582834A - 用于汞脱除的保护吸附剂及其制备和使用方法 - Google Patents
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Abstract
从流体料流中除去汞和/或硫的方法,其包括使流体料流与包含芯和多孔外壳的吸着剂接触,形成所述多孔外壳以包含延伸通过其中并与芯连通的多个孔。芯包含选自由碱性铜含氧盐、铜氧化物和硫化铜组成的组的铜化合物。
Description
早期国家申请的优先权要求
本申请要求2012年2月6日提交的美国申请No.13/367,345的优先权。
发明领域
本公开内容一般性地涉及从烃液体或气体料流中除去污染物。在某些实施方案中,本公开内容涉及使用铜基吸着剂从烃料流中除去汞。在某些实施方案中,本公开内容涉及保护的且高负荷的铜基吸着剂芯从烃料流中除去硫和/或汞的用途。
发明背景
烃流体料流,包括液流和气流通常被硫和汞化合物污染。包含负载型金属硫化物如硫化铜(CuS)的吸着剂用于从烃流体料流中清除汞。例如,美国专利No.4,094,777描述了包含载体和铜硫化物的固体物质作为来自气体或液体的汞的吸收剂。用于Hg脱除的CuS基材料由Axens,JohnsonMatthey(JM)及其它提供以用于天然气和烃工业中。
包含负载型金属氧化物如氧化铜(CuO)的吸着剂用于从烃流体料流中除去硫和汞。例如,美国专利No.7,645,306描述了包含铜氧化物(CuO)的吸着剂吸附硫和汞。
发现从流体料流中清除的汞集中在铜基吸着剂的表面上,产生薄富汞外壳。因而,现有技术吸着剂遭遇至少两个问题。第一,含汞外壳是脆的且倾向于容易从吸着剂上脱离,导致产生富汞颗粒。所得颗粒产生安全性和环境危害。例如,放置期间饱和吸着剂珠的运动可导致汞释放到环境中。另外,生产使用期间,例如床扰动、摩擦或工艺扰乱期间颗粒物的释放会产生提高的压降,因为释放的颗粒物干扰吸着剂珠周围的材料流动。
第二,仅活性铜材料的外部用于汞清除,产生差的活性组分利用。因此,需要(i)能够保持其结构并且较少可能流出富汞颗粒,和(ii)具有较高活性组分利用水平的汞或硫/汞吸着剂。
发明概述
提出从流体料流中除去汞和/或硫的方法。该方法包括使流体料流与具有芯和外壳的吸着剂接触,形成所需外壳以包含延伸通过其中并与芯连通的多个孔。芯进一步包含铜化合物。
还提出吸附剂颗粒。吸附剂颗粒包含含有铜化合物的芯和置于芯上的多孔外壳。形成多孔外壳以包含延伸通过其中并与芯连通的多个孔。多孔外壳不包含铜化合物。
附图简述
图1为在使用以前,申请人的吸着剂的简化横截面;和
图2为在暴露于含汞料流以后,申请人的吸着剂的简化横截面。
优选实施方案详述
在以下描述中参考附图以优选实施方案描述本发明,其中类似的数字表示相同或类似的元件。在整个该说明书中,关于“一个(one/an)实施方案”或类似语言的提及意指关于该实施方案描述的特定特征、结构或特性包括在本发明的至少一个实施方案中。因此,在整个该说明书中,短语“在一个(one/an)实施方案中”和类似语言可以,但未必都指相同的实施方案。
如本文所用术语吸着剂、吸附剂和吸收剂指材料吸收或吸取其表面上的液体或气体组分或者将这类组分吸收到其本体中的能力。
现有技术吸着剂通常由遍及多孔金属氧化物载体如氧化铝布置的碱式碳酸铜、铜氧化物或铜硫化物材料组成,并成型成珠。吸着剂中的铜硫化物与流体中的汞通过反应(1)反应以产生硫化汞(HgS)。
2CuS+Hg→HgS+Cu2S (1)
当用于含硫流体料流中时,铜氧化物通过反应(2)转化成铜硫化物,铜硫化物然后借助反应(1)与汞反应。
CuO+H2S→CuS+H2O (2)
铜氧化物与硫和汞的总反应显示于反应(3)中。
2CuO+Hg+2H2S→HgS+Cu2S+2H2O (3)
在可选反应中,碱式碳酸铜如反应(4)所示与H2S反应。
Cu2(OH)2CO3+2H2S→2CuS+CO2+3H2O (4)
所得CuS然后根据反应1与料流中的汞反应。在这种情况下,总反应显示于反应(5)中。
Cu2(OH)2CO3+2H2S+Hg→HgS+Cu2S+CO2+3H2O (5)
观察到汞主要被吸收在吸着剂的表面上以形成富汞外壳。即使活性组分(即CuS)遍及吸收剂地分散,仅吸着剂表面附近的一部分活性材料与汞反应。因而,未利用吸着剂珠内部的活性材料。
另外,根据现有技术制备的高负载吸收剂遭遇大量缺点。第一,活性铜组分的增加(即更重负载的吸着剂)会产生更大的含汞颗粒形成的潜能,因为在形成以后较少的载体材料保护含汞外壳。第二,活性铜与载体材料的比的提高降低了使用以前吸着剂的结构完整性,产生降低的压碎强度、增加的颗粒形成和较低的操作性能。
在一个实施方案中,申请人的吸着剂包含围绕芯的多孔外壳,芯包含活性材料。申请人的吸着剂的多孔外壳提供容许高负载铜芯的结构支持。在一个实施方案中,申请人的吸着剂的多孔外壳仅包含载体材料,因此包括具有比现有技术含铜吸着剂更高的压碎强度的吸着剂。
在某些实施方案中,申请人的吸着剂包含小且高负载的铜芯。在某些实施方案中,芯包含置于载体材料内的含铜活性组分。高度多孔材料置于芯上以形成外壳。外壳具有分级以容许含汞和/或含硫化合物进入吸着剂中并接触芯中的含铜活性组分的孔。当清除汞时,在吸着剂内在芯与高度多孔外壳之间的界面上形成富汞层。因此,高度多孔外壳围绕和保持脆性富汞层并防止含汞颗粒的释放。
在各个实施方案中,申请人的吸着剂用于从烃流体(即液体或气体)料流中除去元素汞。在各个实施方案中,申请人的吸着剂用于从烃流体(即液体或气体)料流中除去硫和含硫化合物(集合性地,硫),例如但不限于H2S和/或硫醇。
参考图1,描述了申请人的吸着剂珠的横截面的简化图100。包含负载铜硫化物的芯102置于多孔外壳104内。多个孔106延伸通过外壳并与芯连通,由此容许污染物材料通过多孔外壳104并接触芯102。所述孔106简化用于解释且应当不解释为限定性的。如本领域技术人员所理解,多孔外壳中的孔是通常彼此交叉的不规则形状通道。芯具有直径108且多孔外壳具有外径110。在某些实施方案中,芯直径108与多孔外壳直径110(即吸着剂的外径)之间的比为0.3-0.99。在某些实施方案中,多孔外壳直径110为0.5-20mm。在某些实施方案中,多孔外壳直径110为1.5-10mm。
在某些实施方案中,申请人的吸着剂芯为铜化合物。在某些实施方案中,申请人的吸着剂芯包含置于载体材料内的铜化合物。在各个实施方案中,吸着剂芯包含置于载体材料内的铜含氧盐,例如但不限于碱式碳酸铜。在各个实施方案中,吸着剂芯包含置于载体材料内的铜氧化物和卤化物盐。在各个实施方案中,吸着剂芯包含置于载体材料内的铜硫化物。在各个实施方案中,吸着剂芯包含置于载体材料内的铜硫化物和卤化物盐。在某些实施方案中,铜硫化物为硫化铜(CuS)。在某些实施方案中,铜硫化物为硫化亚铜(Cu2S)。在某些实施方案中,铜氧化物为氧化铜(CuO)。在某些实施方案中,铜氧化物为氧化亚铜(Cu2O)。
在各个实施方案中,载体材料为选自由氧化铝、二氧化硅、二氧化硅-氧化铝、硅酸盐、铝酸盐、硅铝酸盐如沸石、二氧化钛、氧化锆、赤铁矿、二氧化铈、氧化镁和氧化钨组成的组的金属氧化物。在一个实施方案中,载体材料为氧化铝。在一些实施方案中,载体材料为碳或活性炭。在某些实施方案中,申请人的吸着剂不包含粘合剂。
在各个实施方案中,氧化铝载体材料以过渡型氧化铝的形式存在,其包含能够快速再水化并可以反应性形式保留实质量的水的弱结晶氧化铝相如“ρ”、“χ”和“伪γ”氧化铝的混合物。氢氧化铝Al(OH)3如三水铝石是制备过渡型氧化铝的来源。制备过渡型氧化铝的现有技术工业方法包括将三水铝石研磨至1-20μm的粒度,其后快速煅烧短的接触时间,如专利文献如美国专利No.2,915,365所述。无定形氢氧化铝和其它天然发现的矿物结晶氢氧化物如三羟铝石和诺三水氧化铝或一氧化物氢氧化物(monoxide hydroxide)、AlOOH如勃姆石和水铝石也可用作过渡型氧化铝的来源。在一个实施方案中,该过渡型氧化铝材料的BET表面积为300m2/g,且平均孔径为45埃,如通过氮吸附法测定。
在各个实施方案中,过渡金属的固体含氧盐用作吸着剂芯的起始组分。在某些实施方案中,固体含氧盐在随后的加工步骤中转化成其它铜化合物。在其它实施方案中,所有或一部分固体含氧盐保留在最终吸着剂产物中。通过定义,“含氧盐”指含氧酸的任何盐。有时该定义加宽至“包含氧以及给定阴离子的盐”。FeOCl例如被认为是根据该定义的含氧盐。
在某些实施方案中,含氧盐包含一种或多种铜碳酸盐。碱式碳酸铜如Cu2CO3(OH)2例如可通过铜盐如Cu(NO)3、CuSO4和CuCl2随碳酸钠沉淀而制备。在一个实施方案中,由Phibro Tech,Ridgefield Park,N.J.生产的合成形式的孔雀石,碱式碳酸铜用作吸着剂芯的组分。
取决于所用条件,尤其是取决于洗涤所得沉淀物,最终材料可包含一些来自沉淀方法的残留产物。在CuCl2原料的情况下,氯化钠是沉淀方法的副产物。申请人发现具有残留氯和钠的市售碱式碳酸铜显示出与实际上无氯的其它商业碱式碳酸铜相比对加热而言较低的稳定性和对还原而言改进的抗性。
在一个实施方案中,碱式碳酸铜颗粒的粒度在过渡型氧化铝范围内,即1-20μm。在其它实施方案中,吸着剂芯包含含氧盐蓝铜矿Cu3(CO3)2(OH)2。在其它实施方案中,吸着剂芯包含铜、镍、铁、锰、钴、锌或其混合物的含氧盐。
在某些实施方案中,吸着剂芯通过将无机卤化物添加剂和碱式碳酸铜的混合物煅烧足够的时间以使碱式碳酸铜分解成氧化物而制备。在各个实施方案中,无机卤化物为氯化钠、氯化钾或其混合物。在某些实施方案中,无机卤化物为溴盐。在各个实施方案中,吸着剂芯中的氯化物含量为0.05-2.5质量%。在各个实施方案中,吸着剂芯中的氯化物含量为0.3-1.2质量%。包含卤化物盐的铜氧化物基吸着剂芯显示出比不用卤化物盐制备的类似吸着剂芯更高的耐还原性。在某些实施方案中,卤化物为氯化物。
在某些实施方案中,吸着剂芯通过将铜氧化物材料硫化而制备。例如,在一个实施方案中,通过在150℃下暴露于H2S下而将铜氧化物基吸着剂芯(CuO)硫化以形成铜硫化物基吸着剂芯(CuS)。在一个实施方案中,铜氧化物基吸着剂芯通过被处理的含汞流体料流中的痕量硫硫化。在一个实施方案中,铜氧化物基吸着剂芯在暴露于含汞流体料流下以前硫化。在一些实施方案中,铜氧化物仅部分硫化,产生包含铜氧化物和铜硫化物的吸着剂芯。在各个实施方案中,作为吸着剂芯的百分数计算,吸着剂芯中的含铜材料的百分数为25-90质量%。在各个实施方案中,吸着剂芯中铜化合物(不包括铜硫化物)与铜硫化物的质量比为0.1-0.7。本领域技术人员应当理解可进行其它硫化方法以实现含铜硫化物的吸着剂芯。
在各个实施方案中并取决于应用,吸着剂芯包含基于无挥发物作为CuO计算8-95质量%的铜。在一个实施方案中,吸着剂芯包含基于无挥发物作为CuO计算10质量%的铜。在一个实施方案中,吸着剂芯包含基于无挥发物作为CuO计算40质量%的铜。在一个实施方案中,吸着剂芯包含基于无挥发物作为CuO计算65质量%的铜。在一个实施方案中,吸着剂芯包含基于无挥发物作为CuO计算70质量%的铜。
在一个实施方案中,吸着剂芯通过将碱式碳酸铜与氧化铝共球化,其后固化和活化而制备。在各个实施方案中,球化或团聚在盘或鼓中进行。将材料通过球化机的旋转运动或振动而搅拌,同时用水喷雾以形成珠。在一个实施方案中,将水用足以实现最终干产物中至多0.8质量%氯的浓度的弱氯化钠取代。在一个实施方案中,将珠在60℃下固化并在移动床活化器中在175℃或175℃以下的温度下干燥。在其它实施方案中,吸着剂芯通过挤出形成。在某些实施方案中,吸着剂芯为多孔的,具有运行通过其中的多个空隙和通道。
本领域技术人员应当理解可进行其它方法以实现与申请人的发明相合适的含金属氧化物和/或含金属硫化物的吸着剂芯。
多孔外壳形式的保护涂层置于吸着剂芯上。在一个实施方案中,涂层包含通过美国专利No.6,736,882所述方法将胶态金属二氧化硅施涂于吸着剂芯上而形成的二氧化硅,通过引用将其并入本文中。在各个实施方案中,胶态金属二氧化硅外壳为吸着剂的1-2质量%。在各个实施方案中,胶态金属二氧化硅外壳的厚度为10-150μm。胶态金属二氧化硅外壳为多孔的以容许含汞和/或含硫化合物渗透并与吸着剂芯中的含铜材料反应。另外,与现有技术相比,胶态金属二氧化硅外壳提高吸着剂的结构完整性,防止富汞颗粒的释放,使得能够使用更高度负载铜的吸着剂芯,并且使得能够更高的利用吸着剂芯的活性铜组分。
在一个实施方案中,涂层通过将吸着剂芯与氧化铝共球化而形成。具有变化厚度的高度多孔外壳可以以该方式通过改变但不限于球化方法、球化时间和所用氧化铝的类型而形成。如本领域技术人员所理解,申请人的吸着剂可通过在吸着剂芯上产生高度多孔外壳的其它方法形成。
在各个实施方案中,氧化铝外壳的厚度为100-1500μm。在一个实施方案中,氧化铝外壳的BET表面积为280m2/g,且平均孔径为至少45埃,如通过氮吸附法所测定。在一个实施方案中,涂层为中孔的(即具有直径为2-50nm的孔)。在一个实施方案中,涂层为大孔的(即具有直径>50nm的孔,占总孔体积的至少三分之一)。
在某些实施方案中,氧化铝外壳是大的使得芯仅为吸着剂的3-15质量%。
在某些实施方案中,外壳包含选自由氧化铝、二氧化硅、二氧化硅-氧化铝、硅酸盐、铝酸盐、硅铝酸盐如沸石、二氧化钛、氧化锆、赤铁矿、二氧化铈、氧化镁和氧化钨组成的组的金属氧化物。在一个实施方案中,外壳包含氧化铝。在一些实施方案中,外壳包含碳或活性炭。在某些实施方案中,外壳不包含粘合剂。在某些实施方案中,外壳不包含铜氧化物。
在一些实施方案中,将外壳活化以清除硫或其它杂质。在各个实施方案中,活化包括在外壳中或外壳上形成或并入反应性材料,例如铜氧化物、镍氧化物、铁氧化物、锰氧化物、钴氧化物、锌氧化物或其组合。在一个实施方案中,并入包括在团聚以前或期间将氧化物加入吸着剂芯和氧化铝的混合物中。在某些实施方案中,活化包括将铜硫化物如CuS或Cu2S并入外壳中。在某些实施方案中,反应性材料不包含铜氧化物。
在一些实施方案中,将外壳活化以从流体料流中清除不同于汞的不理想组分如氯。在一些实施方案中,将外壳活化以充当分子筛从流体料流中俘获不同于汞的不理想组分如氯。
氧化铝外壳提供吸着剂的结构支持,由此(i)防止富汞颗粒的释放,(ii)使得能够使用高度负载铜的吸着剂芯,(iii)使得能够利用吸着剂芯的活性铜组分,和(iv)提高吸着剂的压碎强度。在一个实施方案中,吸着剂芯包含大于10质量%铜氧化物且多孔吸着剂外壳不包含铜氧化物。
在一个实施方案中,吸着剂芯为7×14目(2.8mm×1.4mm)或更小。在不同的实施方案中,在形成外壳以后,吸着剂为3×6目(6.7mm×3.3mm)或5×8目(4.0mm×2.4mm)。在不同的实施方案中,吸着剂为大于3×6目(6.7mm×3.3mm)。
如本文所用“A×B目(C mm×D mm)”代表吸着剂颗粒的粒度范围。在该实例中,目用于分离能够通过C mm筛目(即C mm正方形开口),但不能通过D mm筛目(即D mm正方形开口)的吸着剂颗粒。例如7×14目(2.8mm×1.4mm)会捕集具有大于1.4mm且小于2.8mm的最小尺寸的吸着剂珠或不规则形状颗粒。
具有大粒度(例如大于3mm)、大孔外壳(例如至少250m2/g BET表面积,具有如通过压汞法测定为至少0.3cm2/g的总孔体积,且包含具有至少0.08cm2/g的大于50nm大孔)和小吸着剂芯(吸着剂重量的3-15%)的申请人的吸着剂珠特别好地适于其中低压降是理想的应用。在一个实施方案中,这类吸着剂的堆积密度为721kg/m3(45 lbs/ft3)-1281kg/m3(80 lbs/ft3)。在一个实施方案中,这类吸着剂的堆积密度为993kg/m3(62 lbs/ft3)。在一个实施方案中,这类吸着剂的堆积密度为800kg/m3(50 lbs/ft3)。
参考图2,描述了在暴露于流体(即气体或液体)料流以后,具有清除的汞的申请人的吸着剂珠的横截面的简化图200。硫化汞202在芯102和外壳104的交叉处的多个孔106的底部形成。外壳104保护并使芯102和硫化汞202稳定化。因而,含汞化合物在加工和后加工处理期间较少可能由于破裂而释放到吸着剂珠上。另外,外壳104增加了结构支持,赋予吸着剂珠提高的压碎强度。在某些实施方案中,硫化汞由于与如204所示其它硫来源(即不同于芯中的硫化铜形式的硫)反应而在外壳104的孔106内形成。这样形成的硫化汞捕集在外壳中。因此,在一些实施方案中,在暴露于含汞料流以后,申请人的吸着剂的硫化汞的量超过反应(4)施加的理论极限。
2CuS+Hg→HgS+Cu2S (4)
在一个或多个实施方案中,所述本发明特征、结构或特性可以以任何合适的方式组合。在以上描述中,列举大量具体细节以提供对本发明实施方案的彻底理解。然而,相关领域的技术人员会认识到本发明可不用具体细节的一个或多个,或者用其它方法、组分、材料等等实践。在其它情况下,未详细地显示或描述熟知的结构、材料或操作以避免使本发明的方面不清楚。换言之,本发明可以以其它具体形式具体表达而不偏离其精神或基本特性。所述执行在所有方面仅认为是说明性且不是限定性的。因此,本发明的范围应不参考以上描述而确定,而是应参考未决权利要求书以及其完全范围或等价物确定,且在权利要求书的含义和等价范围内的所有变化应当包括在其全部范围内。
Claims (10)
1.从流体料流中除去选自由汞和硫组成的组的至少一种杂质的方法,包括使所述流体料流与包含芯102和多孔外壳104的吸着剂100接触,形成所述多孔外壳以包含延伸通过其中并与所述芯102连通的多个孔106,其中所述芯102包含选自由碱性铜含氧盐、铜氧化物和铜硫化物组成的组的铜化合物。
2.根据权利要求1的方法,其中所述多孔外壳104包含选自由氧化铝、二氧化硅、二氧化硅-氧化铝、硅酸盐、铝酸盐、硅铝酸盐、沸石、二氧化钛、氧化锆、赤铁矿、二氧化铈、氧化镁和氧化钨组成的组的金属氧化物。
3.根据权利要求2的方法,其中所述多孔外壳104不包含铜氧化物。
4.根据权利要求3的方法,其中所述多孔外壳104占所述吸着剂100的1-5质量%。
5.根据权利要求3的方法,其中:
所述芯102为所述吸着剂100的3-30质量%;
所述铜化合物置于金属氧化物基质上;和
所述吸着剂100包含小于800kg/m3(50 lbs/ft3)的堆积密度。
6.根据权利要求3的方法,其中所述铜化合物占所述芯102的8-95质量%。
7.吸附剂颗粒100,其包含:
包含铜化合物的芯102;和
置于所述芯102上的多孔外壳104,其中形成所述多孔外壳104以包含延伸通过其中并与所述芯102连通的多个孔106,且其中所述多孔外壳104不包含铜氧化物。
8.根据权利要求7的吸附剂颗粒100,其中:
所述铜化合物选自由碱性铜含氧盐、铜氧化物和铜硫化物组成的组;和
所述铜化合物置于金属氧化物基质上。
9.根据权利要求8的吸附剂颗粒100,其中所述多孔外壳104为所述吸收剂颗粒100的1-5质量%。
10.根据权利要求8的吸附剂颗粒100,其中:
所述芯102为所述吸着剂100的3-30质量%;且
吸附剂颗粒100包含小于800kg/m3(50 lbs/ft3)的堆积密度。
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WO (1) | WO2013119363A2 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107519836A (zh) * | 2016-06-21 | 2017-12-29 | Ifp 新能源公司 | 具有改进的性能的重金属捕集物质 |
CN107787249A (zh) * | 2015-06-05 | 2018-03-09 | 庄信万丰股份有限公司 | 制备吸着剂的方法 |
CN108249955A (zh) * | 2018-04-02 | 2018-07-06 | 中科京投环境科技江苏有限公司 | 一种脱除废、污水中汞的复合陶瓷材料及制备方法 |
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FR2980721B1 (fr) * | 2011-10-04 | 2015-03-13 | IFP Energies Nouvelles | Mise en forme de masses de captation pour la purification d'une charge gaz ou liquide contenant du mercure |
FR2980722B1 (fr) * | 2011-10-04 | 2015-03-20 | IFP Energies Nouvelles | Masse de captation a performances ameliorees et son utilisation dans la captation de metaux lourds |
GB201213361D0 (en) * | 2012-07-26 | 2012-09-12 | Johnson Matthey Plc | Sorbents |
WO2014134128A1 (en) * | 2013-02-27 | 2014-09-04 | Fuel Tech, Inc. | Processes, apparatus, compositions and systems for reducing emissions of hci and/or sulfur oxides |
JP6858055B2 (ja) * | 2017-03-30 | 2021-04-14 | 水澤化学工業株式会社 | 鉛吸着剤 |
CN108993504B (zh) * | 2018-07-25 | 2021-12-14 | 北京市劳动保护科学研究所 | 一种用于含硫烟气脱汞的改性活性焦及其制备方法 |
WO2022178236A1 (en) | 2021-02-19 | 2022-08-25 | Nissan Chemical America Corporation | Use of transition metal doped nanoparticles and silica nanoparticles for h2s removal |
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- 2013-01-16 EP EP13747289.0A patent/EP2833983A2/en not_active Withdrawn
- 2013-01-16 WO PCT/US2013/021698 patent/WO2013119363A2/en active Application Filing
- 2013-01-16 AU AU2013217739A patent/AU2013217739B2/en not_active Ceased
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2015
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107787249A (zh) * | 2015-06-05 | 2018-03-09 | 庄信万丰股份有限公司 | 制备吸着剂的方法 |
CN107787249B (zh) * | 2015-06-05 | 2021-06-11 | 庄信万丰股份有限公司 | 制备吸着剂的方法 |
CN107519836A (zh) * | 2016-06-21 | 2017-12-29 | Ifp 新能源公司 | 具有改进的性能的重金属捕集物质 |
CN107519836B (zh) * | 2016-06-21 | 2022-06-07 | Ifp 新能源公司 | 具有改进的性能的重金属捕集物质 |
CN108249955A (zh) * | 2018-04-02 | 2018-07-06 | 中科京投环境科技江苏有限公司 | 一种脱除废、污水中汞的复合陶瓷材料及制备方法 |
CN108249955B (zh) * | 2018-04-02 | 2020-12-29 | 中科京投环境科技江苏有限公司 | 一种脱除废、污水中汞的复合陶瓷材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20150217271A1 (en) | 2015-08-06 |
WO2013119363A2 (en) | 2013-08-15 |
AU2013217739B2 (en) | 2015-09-24 |
US20130204065A1 (en) | 2013-08-08 |
EP2833983A2 (en) | 2015-02-11 |
US9006508B2 (en) | 2015-04-14 |
AU2013217739A1 (en) | 2014-08-21 |
WO2013119363A3 (en) | 2015-06-11 |
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