CN105611996B - 用于结合金属的吸附剂及其生产 - Google Patents
用于结合金属的吸附剂及其生产 Download PDFInfo
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- CN105611996B CN105611996B CN201580002141.XA CN201580002141A CN105611996B CN 105611996 B CN105611996 B CN 105611996B CN 201580002141 A CN201580002141 A CN 201580002141A CN 105611996 B CN105611996 B CN 105611996B
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Images
Classifications
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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Abstract
本发明涉及一种适用于从溶液中结合金属的吸附剂,相应的吸附剂的生产以及吸附剂从溶液中结合金属的应用。
Description
技术领域
本发明涉及一种适用于从溶液中结合金属的吸附剂,相应的吸附剂的生产以及吸附剂从溶液中结合金属的的应用。
背景技术
由例如电镀处理的工业废水、来自石油化学或者制药工业的催化剂残渣、例如来自矿山的井下水、重金属污染土地的复原物等等去除或者回收或者回收再利用金属,特别是重金属是越来越重要的任务,因为特别是重金属要么具有对环境有害的作用,要么重金属的回收再利用也呈现经济上的需求。亦即,一方面环境观点很重要,另一方面提供有价值的金属也是很高的需求,因为这些金属的供给越来越成问题或者这些金属的价格上涨。用于去除或者回收或者回收再利用金属或者重金属的吸附剂的另一重要的应用领域是在饮用水处理以及海水脱盐中分离这些金属或者重金属。同样,由浓缩盐溶液分离重金属,例如以氯-碱电解或者类似的方法分离这些重金属,也有很高的需求。
从例如高浓度的或者低浓度的溶液或者强酸性溶液,特别是在碱金属离子或者碱土金属离子的情况下,要结合充足量的金属,迄今已知的相/吸附剂对于提到的应用领域来说经常不具有充分的结合能力。此外,迄今已知的相经常不具有在pH 0至pH 14的整个范围上的稳定性。许多迄今已知的相的另一缺点在于,虽然所期望的金属可以被结合,但是不可以以简单的方式和方法或者甚至完全不可以由被应用的吸附剂再回收。由于已知的吸附剂/相的大多不令人满意的结合能力,经常需要高的吸附剂体积/相体积,由此,金属结合方法是相当昂贵的并且是成本效率低的。此外,由于已知的金属结合吸附剂的大多较小的结合能力,需要多次实施这些方法,以便例如可以作为饮用水提供无重金属的水。
发明内容
因此,本发明的任务在于,提供一种新的吸附剂,该吸附剂部分地或者完全不具有上面提到的缺点。特别是,本发明的任务在于,提供一种具有相对于每克或者每毫升金属、特别是重金属和贵金属的高的结合能力的吸附剂。优选按照本发明提供的吸附剂特别是可利用氢氧化钠除去有害成分的(sanitisierbar),或者允许以简单的方式和方法再回收金属。本发明的另一任务在于,提供一种吸附剂,该吸附剂在酸性条件下也还具有相对高的对金属的结合能力。
此外,应该相对于由现有技术已知的金属结合吸附剂减少用于金属结合的吸附剂的体积。
本发明的任务通过一种吸附剂解决,该吸附剂包括利用含有一氨基的聚合物涂覆的多孔的支承材料载体,其中,基于吸附剂的总体积,通过滴定确定的吸附剂的氨基的浓度至少是600μmol/mL。
在本发明的另一实施形式中,通过滴定确定的吸附剂的氨基的浓度优选至少是800μmol/mL,更大程度优选至少是1000μmol/mL,再大程度优选至少是1200μmol/mL并且最大程度优选至少具有1500μmol/mL吸附剂。通过滴定确定的按照本发明的吸附剂的氨基的浓度的上限通过空间上的可实现性或者在含有氨基的聚合物中氨基的排列的最大的可能的密度受到限制并且处于大约最大4000μmol/mL、更大程度优选3000μmol/mL并且最大程度优选大约2500μmol/mL。在通过滴定确定的吸附剂的氨基的浓度下存在如下浓度,该浓度按照在本申请的示例部分中给出的分析方法通过利用4-甲苯磺酸的穿透测量法获得。
此外优选,按照本发明的吸附剂具有含有氨基的聚合物的质量相对于多孔的支承材料的孔的总体积大于或者等于0.1g/mL的比例,更大程度优选大于或者等于0.125g/mL的比例,再大程度优选大于或者等于0.15g/mL的比例并且最大程度优选大于或者等于0.20g/mL的比例。在这里,提到的比例的上限在这里为物理上的界限,然而优选大约最大为0.5g/mL,更大程度优选大约最大为0.4g/mL并且最大程度优选大约最大为0.3g/mL。
含有氨基的聚合物的质量可以通过相对于支承材料装填密度的增长按照DIN53194确定。多孔的支承材料的孔的总体积[V]可以通过多孔的支承材料的溶剂吸收能力(WAK)确定。同样也可以确定孔体积[Vol.-%]。在此,分别涉及支承材料的可自由进入的孔的体积,因为仅可以通过溶剂吸收能力确定所述体积。溶剂吸收能力给出所需的溶剂的体积,以便完全填充一克干燥的吸附剂(优选固定相)的孔空间。在这里不仅纯水或者含水的介质,而且例如二甲基甲酰胺的有机溶剂可以用作溶剂。如果吸附剂在润湿时增大其体积(膨胀),则自动检测对此耗费的溶剂量。为了测量WAK,利用过量的良好地湿润的溶剂润湿干燥吸附剂的精确称重的量并且将剩余的溶剂从颗粒间隙中通过离心分离去除。在吸附剂的孔内的溶剂被保留。保留的溶剂的质量通过称重确定并且通过体积内的密度换算。吸附剂的WAK报告为每克干燥的吸附剂的体积(mL/g)。
含有氨基的聚合物在多孔的支承材料上的涂覆优选以水凝胶的形式存在。这特别是在于,含有氨基的聚合物具有上面提到的高的氨基浓度。水凝胶当前理解为含有溶剂(优选水)、但是溶剂可溶的聚合物,该聚合物的分子通过化学方式,例如共价或者离子键或者物理方式,例如通过聚合物链的缠结,结合成三维网状结构。通过嵌入的极性的(优选亲水的)聚合物组分聚合物在溶剂(优选水)中在显著的体积增加的情况下膨胀,但是不失去其材料内聚性。由现有技术的水凝胶已知,当干燥水凝胶时,水凝胶部分地不可逆地失去其特性。然而,在本申请中,水凝胶不失去其特性,因为水凝胶通过多孔的支承材料在化学上并且在力学上稳定。当吸附剂在溶剂中膨胀时,亦即,特别是在下面进一步描述的用于从溶液中结合金属的使用期间,含有氨基的涂覆特别是作为水凝胶存在于按照本发明的吸附剂中。
多孔的支承材料优选中孔的或者大孔的支承材料。多孔的支承材料的平均的孔大小优选存在于6nm至400nm的范围内、更大程度优选10至300nm的范围内并且最大程度优选20至150nm的范围内。在给出的范围内的孔大小是重要的,以便确保充分高的结合能力。对于过小的孔大小的情况,含有氨基的聚合物可能在多孔的支承材料表面上堵塞孔并且孔的内部体积不利用含有氨基的聚合物填充。此外,优选的是,相应地基于多孔的支承材料的总体积,多孔的支承材料具有在30至90Vol.-%范围内的孔体积,更大程度优选40至80Vol.-%并且最大程度优选60至70Vol.-%。
多孔的支承材料的平均的孔大小可以通过孔填充方法利用水银按照DIN66133确定。
多孔的支承材料可以包括有机聚合物、无机材料或者由有机聚合物和无机材料组成的复合材料或者由这些材料制成。
为了可以提供在pH 0至pH 14的范围上具有高的吸附稳定性的吸附剂,优选多孔的支承材料是有机聚合物。
用于多孔的支承材料的有机聚合物优选如下:聚链烷,优选在侧链中具有的芳香基(这意味着结合到聚烷基链上)的聚链烷,聚丙烯酸酯,聚甲基丙烯酸酯,聚丙烯酰胺,聚乙烯醇,多糖(例如淀粉、纤维素、纤维素酯、直链淀粉、琼脂糖、交联琼脂糖、甘露聚糖、黄原胶和葡聚糖)以及由此的混合物。有机聚合物最大程度优选是聚苯乙烯或者聚苯乙烯的衍生物,该衍生物优选是由聚苯乙烯(或者聚苯乙烯的衍生物)和二乙烯基苯形成的共聚物。如果有机聚合物具有芳香基,则该有机聚合物优选为磺化的。在一种本发明的完全特别优选的实施形式中,有机聚合物是磺化的交联的聚(苯乙烯-共聚-二乙烯基苯)或者由此的衍生物。
如果多孔的支承材料是无机材料,或者包括无机材料,则无机材料优选为无机矿物氧化物、例如氧化硅、氧化铝、氧化镁、氧化钛、氧化锆、氟硅物(Fluorosil)、磁铁矿、沸石、硅酸盐(例如硅藻土)、云母、羟基磷灰石、氟磷灰石、有机金属基本结构、陶瓷、玻璃、多孔玻璃(例如Trisoperl)、金属、例如铝、硅、铁、钛、铜、银和金、石墨和无定形碳。无机的多孔的支承材料特别是优选为氧化硅或者氧化铝、特别是氧化硅。该氧化硅特别是硅胶。
特别是由于在大的pH范围内、特别是在碱性范围内使用的原因,所述多孔的支承材料优选是有机聚合物。
按照本发明使用的多孔的支承材料可以是均质的或者异质的组合物,并且因此特别是包含由一个或者多个上面提到的材料组合的材料,例如多层组合物。
多孔的支承材料优选是具有在5至2000μm范围内、更大程度优选在10至1000μm范围内的平均颗粒大小的颗粒状的材料。多孔的支承材料也可以是片状的或者纤维状的材料、例如膜片或者泡沫。因此,多孔的支承材料的外表面可以是平坦的(薄片、胶片、圆盘、膜片、纤维织物或者非纤维织物)或者弯曲的(要么凹形的要么凸形的:球形的、微粒、(空心)纤维、管道、毛细管)。
如上面进一步提到的那样,多孔的支承材料以含有氨基的聚合物涂覆,该聚合物由各个高分子链组成或者包括这些高分子链。高分子链优选相互共价地连接。含有氨基的聚合物优选与多孔的支承材料非共价地连接。
此外,将非共价地表面结合的交联的聚合物作为含有氨基的聚合物在多孔的支承材料上使用具有以下三个优点:(1)聚合物的挠性,这是因为聚合物非共价地结合到多孔的支承材料的表面上;(2)含有氨基的聚合物的交联确保薄膜保持在多孔的支承材料表面上并且在使用吸附剂期间不失去;(3)当聚合物非共价地与支承材料结合时,含有氨基的聚合物的厚度可按支承材料相应的大小来选择。
含有氨基的聚合物的充分的挠性和渗透性是重要的,以便多个所述氨基可以获得一种构象,该构象能多次配位地结合金属。
按照本发明的吸附剂或者按照下面提到的按照本发明的方法制造的吸附剂的高的金属结合能力由于以下原因对于发明人来说是令人意外的:
·尽管利用含有氨基的聚合物几乎完全填充支承材料的孔,这些孔由于聚合物的渗透性对于金属是可进入的,由此,按照本发明的吸附剂具有高的金属结合能力。作为来自反相的尺寸排阻色谱法的聚合物标准呈现出无的可进入性或者渗透性,这更令人意外。这对于最小标准以450Da观测超过90%。
·与基于表面功能化的原理的通常的色谱分析的吸附剂和金属结合吸附剂不同,高的金属结合特性以令人意外的方式确定,本发明不仅充分利用该聚合物的表面,也充分利用负责结合的聚合物的总体积,亦即,含有氨基的聚合物与含有金属的溶剂一起形成所谓的水凝胶,在该水凝胶中聚合物网状结构具有纳米孔隙度。这导致金属结合能力不仅由支承材料的表面,而且由施涂的聚合物的体积确定。
·按照本发明的吸附剂或者按照本发明制造的吸附剂的高的金属结合能力由含有氨基的聚合物的基团和要结合的金属之间的化学的复合物的构成决定。所述基团可以是氨基基团本身,或者可以是具有路易斯碱特性的残留物,这些残留物结合到含有氨基的聚合物上(如下面进一步描述的那样)。这例如导致相对于传统的离子交换在酸性环境中高的耐盐性或者结合能力的优点。
·与由其结合金属的化学复合物的构成平行,也进一步具有对于阴离子、例如硫酸盐、碳酸盐、亚硝酸盐、硝酸盐、铬酸盐、砷酸盐等等的相当高的结合能力。
在按照本发明的吸附剂上的含有氨基的聚合物优选是一种聚合物,该聚合物具有伯和/或仲氨基。可以是由相同的重复单元(聚合的单体)组成的聚合物,但是也可以是共聚物,该共聚物作为共聚单体优选具有简单的烯单体或者例如乙烯吡咯烷酮的极性惰性单体。
含有氨基的聚合物的示例如下:聚胺、如所有的聚烷基胺,例如聚乙烯胺和聚丙烯胺、聚乙烯亚胺、聚赖氨酸等等。在所述聚合物下优选聚烷基胺、更大程度地优选聚乙烯胺和聚丙烯胺,其中,特别优选聚乙烯胺。
根据按照本发明的吸附剂的优选的实施形式,相对于在含有氨基的聚合物中可交联的基团的总数量,含有氨基的聚合物具有至少2%的交联度。相应地,相对于在含有氨基的聚合物中可交联的基团的总数量,更大程度优选交联度处于2.5至60%的范围内,再大程度优选处于5至50%的范围内并且最大程度优选处于10至40%的范围内。交联度可以通过交联介质的相应地期望的量来调节。在此假定,100Mol-%的交联介质反应并且形成交联。这可以通过分析方法、例如通过MAS-NMR光谱学和基于使用的吸附剂的量定量确定交联介质的量来检验。按照本发明优选所述方法。然而,交联度也可以通过IR光谱学在使用测定曲线的情况下参照例如C-O-C或者OH振动来确定。两种方法是在该领域内对于本领域技术人员来说分析的标准方法。当交联度处于给出的上限之上时,含有氨基的聚合物的聚合物涂覆不具有充分挠性并且造成更少的金属结合能力。如果交联度在给出的下限之下,则所述聚合物涂覆在多孔的支承材料的表面上不是充分稳定的。
交联介质具有两个、三个或者多个官能团,通过这些官能团到聚合物上的结合进行交联。用于交联含有氨基的聚合物的交联介质优选如下:二羧酸、三羧酸、尿素、双环氧化物或者三环氧化物、二异氰酸酯或者三异氰酸酯、和二卤代烷或者三卤代烷,其中,优选是二羧酸和双环氧化物,例如对苯二甲酸、联苯二甲酸、乙二醇缩水甘油醚和1,12-双-(5-降冰片烯-2,3-二甲酰亚胺基)-癸烷二羧酸,其中,特别优选乙二醇缩水甘油醚和1,12-双-(5-降冰片烯-2,3-二甲酰亚胺基)-癸烷二羧酸。交联介质在本发明的实施形式中优选是具有4至20个原子之间的长度的线性的构象挠性的分子。
按照本发明的吸附剂的含有氨基的聚合物的优选的分子量优选处于5000至50000g/mol的范围内,这特别是适用于使用的聚乙烯胺。
按照本发明的吸附剂在另一实施形式中也可以具有有机残留物,这些有机残留物结合到含有氨基的聚合物上并且具有路易斯碱的特性。在此特别优选,一种有机残留物结合到含有氨基的聚合物的一个氨基上。在此特别优选,有机残留物结合到其上的氨基在结合之后是仲氨基,以便该氨基也还充分地具有路易斯碱性,而不形成空间位阻。
在另一实施形式中本发明也涉及一种用于生产吸附剂、特别是按照本发明的吸附剂的方法,该方法具有以下步骤(优选以给出的顺序):
(a)提供多孔的支承材料;
(b)将含有氨基的聚合物通过孔填充方法施涂到多孔的支承材料上;
(c)去除在孔填充方法中使用的溶剂;
(d)重复步骤(b)和(c),以及
(e)交联含有氨基的聚合物。
在用于生产吸附剂的按照本发明的方法中,在步骤(a)中提供的多孔的支承材料如在上面按照本发明的吸附剂相关联地提到的那样。在那里提到的优选的实施形式在这里以相同的程度适用。
在按照本发明的方法的步骤(b)中优选使用非交联的含有氨基的聚合物,如在上面与按照本发明的吸附剂的含有氨基的聚合物相关联地提出的那样。在那里提出的优选的实施形式在这里以相同的程度适用。
在按照本发明的方法中将含有氨基的聚合物施涂到多孔的支承材料上的步骤(b)中的孔填充方法相对于传统的浸渍方法具有如下优点,即,在整体上可以将更大量的含有氨基的聚合物施涂到多孔的支承材料上,由此提高对金属的结合能力。这导致上面给出的令人意外的优点。
孔填充方法一般理解为特殊的涂覆方法,在该涂覆方法中溶液将含有氨基的聚合物以等于多孔的支承材料的孔的总体积的量施涂到多孔的支承材料上。在此,多孔的支承材料的孔的总体积在步骤(b)、亦即第一次施涂中如上面给出的那样提前确定。
在按照本发明的方法的步骤(c)中用于孔填充方法的溶剂优选通过在40℃至90℃,更大程度优选50℃至70℃并且最大程度优选50至60℃范围内的温度下干燥材料来去除。在此,特别是在0.01至1巴范围内的压力下干燥,更大程度优选在0.1至0.5巴范围内的压力。
用于生产吸附剂的按照本发明的方法的关键步骤在于,在干燥或者去除通过孔填充方法第一步骤施涂的溶剂之后的步骤(d)重复将含有氨基的聚合物通过孔填充方法施涂到多孔的支承材料上的步骤(b)和(c)。对此,在步骤(b)之后通过润湿的和干燥的材料的称重差值确定孔的总体积,该总体积提供用于含有氨基的聚合物到多孔的支承材料上的重复施涂。此外,在按照本发明的方法的另一实施形式中优选,至少重复两次步骤(b)和(c)。在第二次重复步骤(b)和(c)之前也通过润湿的和干燥的材料的称重差值确定提供用于孔填充方法的孔的总体积。步骤(b)和(c)的重复优选以给出的顺序进行。
在施涂含有氨基的聚合物的步骤之后,在步骤(e)中进行含有氨基的聚合物的交联,优选通过与按照本发明的吸附剂相关联地给出的交联介质。所有在上面与按照本发明的吸附剂相关联地给出的涉及交联的特征对用于生产的按照本发明的方法也适用。
此外优选,在通过孔填充方法将含有氨基的聚合物施涂到多孔的支承材料上的多次步骤之间不进行含有氨基的聚合物的交联。
相应地去除在孔填充方法中使用的溶剂优选通过在犁铧式干燥机中的干燥来进行,因为由此可以明显地加速所述步骤。
在另一实施形式中在按照本发明的方法中,步骤(b)和(c)在步骤(e)之前这样经常重复,使得各自基于吸附剂的总体积,在步骤(e)之后通过滴定确定的吸附剂的氨基的浓度至少是600μmol/mL,更大程度优选至少800μmol/mL,再大程度优选至少1000μmol/mL并且最大程度优选至少1200μmol/mL。在上面与按照本发明的吸附剂相关联地给出的吸附剂的氨基的浓度的上限也是在按照本发明的方法中优选的上限。
在按照本发明的方法的另一实施形式中优选,在步骤(d)之后含有氨基的聚合物的质量与多孔的支承材料的孔的总体积的比例大于或者等于0.1g/mL,更大程度优选大约或者等于0.125g/mL,并且最大程度优选大于或者等于0.15g/mL。所述比例的上限优选处于最大0.5g/mL,更大程度优选最大0.4g/mL并且最大程度优选最大0.3g/mL。
在按照本发明的方法的步骤(b)中的孔填充方法中,优选使用一种溶剂作为用于含有氨基的聚合物的溶剂,在该溶剂中含有氨基的聚合物是可溶的。含有氨基的聚合物在按照本发明的方法的步骤(b)中用于孔填充方法的溶剂中的浓度优选处于5g/L至200g/L,更大程度优选10g/L至180g/L,最大程度优选30至160g/L的范围内。低于给出的下限的浓度具有如下缺点,即,必须过于经常地实施步骤(b)和(c),以便达到通过滴定确定的所期望的吸附剂的氨基的浓度,该浓度确保对金属的充分的结合能力。高于给出的上限的浓度不能确保聚合物可以以充分的程度渗透到多孔的支承材料的孔中。
在按照本发明的另一实施形式中优选,在步骤(f)中(优选在步骤(e)之后)将有机残留物结合到含有氨基的聚合物上,该有机残留物具有路易斯碱的特性。此外,在这里优选,在结合有机残留物之后氨基作为仲氨基存在,以便不失去有机残留物的路易斯碱性并且不出现对于氨基对金属的结合的空间位阻。具有路易斯碱的特性的有机残留物理解为达到与要结合的金属进行络合的特别的残留物。
具有路易斯碱性的有机残留物例如具有这样的带有自由电子对的杂原子,例如N、O、P、As或者S。
所有在上面与按照本发明的吸附剂相关联地提到的优选的实施方式以相同的程度适用于按照本发明的方法生产的吸附剂,或者适用于在按照本发明的方法中使用的成分。
在另一实施形式中,本发明也涉及一种吸附剂,该吸附剂可以按照本发明的方法获得,特别是一种可以按照本发明的方法获得的吸附剂,其中,在步骤(f)中有机残留物结合到含有氨基的聚合物上,该有机残留物具有路易斯碱的特性。这样的吸附剂可以通过利用有机残留物的功能化也具有低于上面给出的界限的、通过滴定确定的吸附剂的氨基的浓度,然而特别是其特征在于,通过在按照本发明的方法中一次或者多次重复步骤(b)和(c),支承材料的可自由接近的孔基本上完全利用含有氨基的聚合物填充(当WAK小于0.5Gew.(重量)-%时,这可以达到),或者含有氨基的聚合物的质量与多孔的支承材料的比例在步骤(d)之后处于上面给出的范围内。这样的具有有机残留物(该有机残留物具有路易斯碱的特性)的吸附剂应该也属于这样的吸附剂,所述吸附剂在由含有氨基的聚合物去除有机残留物之后基于吸附剂的总体积具有通过滴定确定的至少600μmol/mL的吸附剂的氨基的浓度。
本发明的另一实施形式涉及吸附剂从溶液中结合金属的用途,其中,所述吸附剂要么是以含有氨基的聚合物涂覆的多孔的支承材料,其中,通过滴定确定的吸附剂的氨基的浓度至少为300μmol/mL,+-更大程度优选400μmol/mL并且再大程度优选500μmol/mL,要么,其中,所述吸附剂是可以按照本发明的方法获得的吸附剂。
换言之,本发明也涉及一种在使用吸附剂的情况下从溶液中结合金属的方法,其中,所述吸附剂要么是以含有氨基的聚合物涂覆的多孔的支承材料,其中,通过滴定确定的吸附剂的氨基的浓度至少为300μmol/mL,更大程度优选400μmol/mL并且再大程度优选500μmol/mL,要么,其中,所述吸附剂是可以按照本发明的方法获得的吸附剂。
按照本发明,应该从其结合金属的溶液可以是浓缩的或者稀释的含水或者无水的、酸性的、碱性的或者中性的溶液。
本申请的金属优选是如下金属,所述金属以离子的形式或者也作为金属配位化合物以离子的形式存在于提到的溶液中。所述金属优选是络合的金属,亦即,可以达到金属配位化合物的金属。所述金属更大程度优选是过渡金属或者稀土金属,再大程度优选贵金属或者稀土元素。所述金属完全特别优选是铜、镍和铬。
在按照本发明的使用的另一实施形式中,应该由其结合金属的溶液是具有至少5g/l碱离子的含盐量。
此外,应该从其结合金属的溶液优选是含水的溶液、特别是具有pH值≤5、更大程度优选≤4并且再大程度优选≤3的的酸性含水溶液。
为了从溶液中结合金属,含金属的溶液与按照本发明的吸附剂接触。这例如可以在传统的柱中发生。在此,按照本发明的吸附剂也可以相互混合地存在,这些吸附剂研发用于结合不同的金属。这通常通过不同的有机残留物对含有氨基的聚合物的结合来进行。
类似地,可以以分批方法实施按照本发明的吸附剂与含有金属的溶液的接触,亦即,不是溶液经过具有吸附剂的容器,而是以吸附剂悬浮在溶液中的形式。
附图说明
现在,应该借助于以下附图和实施例阐述本发明,然而仅示例性地考虑这些附图和实施例:
附图的示图中:
图1和2:图1和2示出在从按照实施例2的含水的溶液结合铜时实施例1与对比实施例1的吸附剂的等温线的对比;
图3:图3示出实施例1的吸附剂对于金属铜、镍和铬的与按照实施例3的金属浓度有关的金属结合能力;
图4:图4示出在按照实施例4的NaCl的不同浓度的情况下每吸收剂的量[kg]所吸收的铜的量[g];
图5和6:图5和6示出对于实施例1的吸附剂吸收铜的实施例5的时间曲线;
图7:图7示出在按照实施例6的若干周期之后吸附剂再生之后对于铜的结合能力;
图8:图8示出按照实施例7的多次涂覆的吸附剂与一次涂覆的吸附剂的铜结合的对比。
具体实施方式
实施例部分:
分析方法:
以利用4-甲苯磺酸的穿透测量法确定吸附剂的氨基的浓度(滴定分析):
动态的阴离子交换能力利用要检验的固定相的柱确定。为此,首先将所有可交换的阴离子在柱中与三氟乙酸酯交换。接着,利用含水的甲苯-4-磺酸试剂洗脱柱,直至所述溶液重新以相同的浓度在柱的端部处逸出(穿透)。由甲苯-4-磺酸溶液的浓度、流动速率和在色谱图中的穿透面积计算由柱结合的甲苯-4-磺酸的量。因此确定的甲苯-4-磺酸的量标定了吸附剂的氨基的浓度。
对于甲苯-4-磺酸在水中的动态的阴离子交换能力基于相体积并且以每升mmol(mM/L)记录。
实施例1:按照本发明的吸附剂的生产:
将200g磺化聚苯乙烯/二乙烯基苯支承材料(平均孔大小30nm)称出到容器中。所述材料具有由1.48mL/g WAK确定的孔体积。在第一次涂覆中将孔体积填充至95%。准备用于涂覆的聚合物溶液。以108g水稀释165.3g聚乙烯胺溶液(固体含量12.1Gew.-%)。以7mL浓盐酸将溶液的pH值调节到9.5。将聚合物溶液提供给支承体并且借助于顶端振荡器混合3h(小时)。接着,经涂覆的支承体在50℃时在真空干燥箱中在25mBar时干燥48h。材料通过干燥失去197.7g水。所述材料第二次被涂覆。此外,以6.8mL浓盐酸将165.0g聚乙烯胺溶液(固体含量12.1Gew.-%)调节到9.5pH值并且以20g水稀释。将聚合物溶液提供给支承体并且借助于顶端振荡器混合3h。接着,经涂覆的支承体在真空干燥箱中在50℃25mBar下干燥48h。材料通过干燥失去181.2g水。所述材料第三次被涂覆。此外,以7.1mL浓盐酸将165.2g聚乙烯胺溶液(固体含量12.1%)调节pH值到9.5并且以5g水稀释。将聚合物溶液提供给支承体并且借助于顶端振荡器混合3h。接着,所述相在50℃和25mBar下在真空干燥箱中干燥至质量恒定。
所述材料在3个步骤中以共计每mL孔体积0.20g PVA被涂覆。
经干燥的材料在双夹套反应器中悬浮在1.5L异丙醇中并且与24.26g乙二醇缩水甘油醚在55℃下在6h内交联。
利用以下溶剂洗涤经涂覆的材料:600mL异丙醇、3600mL 0.1M HCl、1800mL水、1800mL 1M NaOH、1800mL水、1800mL甲醇。
接着,干燥所述材料。获得275g经干燥的材料。
分析:通过滴定确定的氨基的浓度为963μmol/mL。
对比实施例1:传统的吸附剂的生产:
传统的吸附剂是利用2-氨乙基乙基硫醚改性的、具有大于45μm的颗粒尺寸的硅胶((Si)-CH2-CH2-S-CH2-CH2-NH2)(生产厂商:Phosphonics,供货商Sigma-Aldrich,订货号码:743453-10G;0.8-1.3mmol/g填装)。
所述改性可以通过硅胶与3-巯丙基-三甲氧基硅烷的反应和接着与乙亚胺的反应来进行。
实施例2:按照实施例1和对比实例1生产的吸附剂对于从含水的溶液结合铜的应用。
为了记录在图1和2中的等温线实施如下步骤:
10份各大约100mg吸附剂的样品被精确地称出并且分别利用不同浓度的含水量不同的Cu-II溶液(例如CuSO4)培养至少1.5h。滤出所述吸附剂并且光度测定地确定溶液中的Cu-II浓度。由残留的铜的浓度计算被结合的铜的量并且完成等温线。
由在图1和2中的等温线的对比可看出,按照本发明的吸附剂具有比传统的吸附剂明显更高的结合能力。由按照本发明的吸附剂的近似的矩形等温线可看出,所述吸附剂呈现在没有实际的平衡调整的情况下的相当强的结合。这也允许从很稀的溶液几乎完全去除重金属。
实施例3:按照实施例1生产的吸附剂对于从溶液中结合三种过渡金属镍、铜和铬的应用:
各10份限定量的吸附剂的样品被精确地称出并且分别利用不同浓度的含水量不同的金属溶液培养至少1.5h。滤出所述吸附剂并且光度测定地或者利用按照Hach-Lange的金属测定方法(优选光度测定地)确定溶液中的金属浓度。由残留的金属的浓度计算被结合的金属的量并且完成等温线。
由图3可看出,按照本发明的吸附剂以很高的程度结合金属镍(~70mg/g吸附剂)、铜(~120mg/g吸附剂)和铬(~80mg/g吸附剂)。对于具有金属钯、铅和铱的溶液也可以呈现相同的程度。
实施例4:按照实施例1生产的吸附剂对于从具有高的含盐量的溶液结合金属的应用:
5份大约100mg吸附剂的样品被精确地称出并且分别利用各一份Cu溶液(例如CuSO4*5H2O=50mg/ml水)培养至少0.5h,这5份溶液含有0M NaCl、0.01M NaCl、0.1M NaCl、0.5M NaCl和1M NaCl。接着,滤出所述吸附剂并且光度测定地确定滤液中的铜浓度。由残留的金属的浓度计算被结合的铜的量并且完成等温线。
正如由图4可见的那样,在浓度不超过1M食盐时对铜的结合能力本身处于>100mgCu/g吸附剂。这呈现一种非离子的结合机制,该结合机制因此与“标准的”离子交换明显不同。
不存在围绕铜与非复合钠的结合位置的竞争。因此,保持对铜的结合能力。
所述特性允许在处理饮用水、地面水、井下水、污水、海水脱盐设备、氯化钾电解等等中的相的应用,而不受普遍存在并且大过量的碱金属和碱土金属的干扰。
实施例5:按照实施例1生产的吸附剂的结合速度:
具有各大约100mg所述相的样品被精确地称出并且利用Cu溶液(例如CuSO4*5H2O=50mg/ml水)在给出的时间间隔内培养。接着,滤出所述吸附剂并且光度测定地确定滤液中的铜浓度。由残留的金属的浓度计算被结合的铜的量。
图5和6示出相对于时间的从溶液中对铜的结合。在大致90分钟之后铜占据吸附剂的所有结合位置。浓度的变化在48小时之后也不可观测。
实施例6:按照实施例1生产的吸附剂的再利用性:
称量实施例1的1g吸附剂并且处理如下:
1.以1M NaOH(3*5ml)洗脱;
2.水(3*5ml洗脱);
3.添加50ml Cu(比如CuS04*5H20,50mg/ml);
4.培养90min(分钟);
5.过滤
6.(光度测定地)确定滤液中的浓度并且计算被结合的铜的量;
7.重复所述程序。
正如图7可看出的那样,在吸附剂的再生和再利用的10次循环之后对铜的结合能力在10次循环(具有例外循环5和6)之后本身在以5M HCl和1M NaOH处理时保持未减弱的。
实施例7:多次涂覆的吸附剂与一次涂覆的吸附剂的对比:
在硅支承体上生产一次涂覆的吸附剂:
将100g硅胶AGC D-50-120A(平均孔大小12nm)称出到容器中。所述材料具有由1.12mL/g WAK确定的孔体积。准备用于涂覆的聚合物溶液。以20g水稀释79.6g聚乙烯胺溶液(固体含量11.3Gew.-%)。以3mL浓盐酸将溶液的pH值调节到9.5。聚合物溶液作为支承体给出并且在筛选机上混合6h。接着,经涂覆的支承体在50℃下在真空干燥箱中在25mBar下干燥48h。
所述材料以每mL孔体积0.08g PVA被涂覆。
经干燥的材料在双夹套反应器中悬浮在0.5L异丙醇中并且与3.64g乙二醇缩水甘油醚在55℃下在6h内交联。
利用以下溶剂洗涤经涂覆的材料:400mL异丙醇、1200mL 0.1M HCl、400mL水、800mL在水中的0.5M三聚乙胺、600mL水、600mL甲醇。
接着,干燥所述材料。获得108.0g经干燥的材料。
分析:通过滴定确定的氨基的浓度为593μmol/mL。
在硅支承体上生产两次涂覆的吸附剂:
将250g硅胶AGC D-50-120A(平均孔大小12nm)称出到容器中。所述材料具有由1.12mL/g WAK确定的孔体积。准备用于涂覆的聚合物溶液。以60g水稀释200g聚乙烯胺溶液(固体含量11.3Gew.-%)。以7.5mL浓盐酸将溶液的pH值调节到9.5。聚合物溶液作为支承体给出并且在筛选机上通过振动混合6h。接着,经涂覆的支承体在50℃下在真空干燥箱中在25mBar下干燥48h。材料通过干燥失去230g水。所述材料第二次被涂覆。此外,以6.8mL浓盐酸将200g聚乙烯胺溶液(固体含量11.3Gew.-%)调节到9.5pH值并且以23g水稀释该聚乙烯胺溶液。聚合物溶液作为支承体给出并且再次在筛选机上通过振动混合6h。接着,经涂覆的支承体在50℃下在真空干燥箱中在25mBar下干燥48h。
所述材料以每mL孔体积0.16g PVA被涂覆。
经干燥的材料在双夹套反应器中悬浮在1.5L异丙醇中并且与18.2g乙二醇缩水甘油醚在55℃时在6h内交联。
利用以下溶剂洗涤经涂覆的材料:1000mL异丙醇、3000mL 0.1M HCl、1000mL水、2000mL在水中的0.5M三乙胺、1500mL水、1500mL甲醇。
接着,干燥所述材料。获得308g经干燥的材料。
分析:通过滴定确定的氨基的浓度为1254μmol/mL。
在硅支承体上生产三次涂覆的吸附剂:
将250g硅胶AGC D-50-120A(平均孔大小12nm)称出到容器中。所述材料具有由1.12mL/g WAK确定的孔体积。准备用于涂覆的聚合物溶液。以60g水稀释199g聚乙烯胺溶液(固体含量11.3Gew.-%)。以7.6mL浓盐酸将溶液的pH值调节到9.5。聚合物溶液作为支承体给出并且在筛选机上通过振动混合6h。接着,经涂覆的支承体在50℃下在真空干燥箱中在25mBar下干燥48h。材料通过干燥失去231g水。所述材料第二次被涂覆。此外,以7.0mL浓盐酸将200g聚乙烯胺溶液(固体含量11.3Gew.-%)调节到9.5pH值并且以24g水稀释该聚乙烯胺溶液。聚合物溶液作为支承体给出并且再次在筛选机上通过振动混合6h。接着,经涂覆的支承体在50℃时在真空干燥箱中在25mBar时干燥48h。材料通过干燥失去210g水。所述材料第三次被涂覆。此外,以7.0mL浓盐酸将199g聚乙烯胺溶液(固体含量11.3Gew.-%)调节到9.5pH值并且以4g水稀释该聚乙烯胺溶液。聚合物溶液作为支承体给出并且在筛选机上混合6h。接着,经涂覆的支承体在50℃下在真空干燥箱中在25mBar下干燥48h。
所述材料以每mL孔体积0.24g PVA被涂覆。
经干燥的材料在双夹套反应器中悬浮在1.5L异丙醇中并且与27.3g乙二醇缩水甘油醚在55℃下在6h内交联。
利用以下溶剂洗涤经涂覆的材料:1000mL异丙醇、3000mL 0.1M HCl、1000mL水、2000mL在水中的0.5M三乙胺、1500mL水、1500mL甲醇。
接着,干燥所述材料。获得330g经干燥的材料。
分析:通过滴定确定的氨基的浓度为1818μmol/mL。
图8明确地示出,在两次和三次涂覆的吸附剂中的结合能力相对于在一次涂覆的吸附剂中的结合能力急剧增加。
对比实施例2:按照DE 10 2011 107 197 A1的实施例2的吸附剂的生产:
将Rohm&Haas的琥珀铬CG1000S用作吸附剂的基础。如下地磺化所述吸附剂:对此,将165mL浓H2SO4提供到可恒温处理的250mL反应器中。向硫酸提供30.0g支承材料并且以各20mL浓硫酸再次冲洗称重长颈瓶三次。在加入支承材料之后搅拌悬浮物并且以80℃恒温处理。在3h反应时间之后,由反应器排出悬浮物并且分配到两个150mL的注射器上。吸出硫酸并且依次以200mL稀释的(62%的)硫酸、125mL水、175mL甲醇、125mL水并且接着以175mL甲醇洗脱所述相。所述相被吸干并且接着在50℃下在真空中被干燥。由完成的磺化的聚苯乙烯通过称量经干燥的、磺化的聚苯乙烯的方式确定吸水能力或者孔体积,将相同体积的水与该聚苯乙烯混合并且接着离心分离多余的水。在此,处于孔中的水保持在其位置处。
为了涂覆聚苯乙烯,准备含水的聚乙烯胺溶液,该聚乙烯胺溶液由具有35000g/mol的平均摩尔质量的聚乙烯胺制成。将pH值调节到9.5。在此,聚乙烯胺的量为要涂覆的聚苯乙烯的15%,并且溶液的体积为确定的聚苯乙烯的孔体积的95%。聚乙烯胺溶液与聚苯乙烯一起提供到稳定关闭的PE烧瓶中并且在筛式振荡器上在高频率时振荡6小时。在此,必须注意充分混合均匀。在所述步骤之后聚乙烯胺溶液在聚苯乙烯的孔中作用。接着,在50℃在真空干燥箱中将聚苯乙烯干燥至质量恒定。
为了交联聚乙烯胺,将涂覆的聚苯乙烯在三倍体积的异丙醇中吸收并且相对于聚乙烯胺的氨基数与5%的乙二醇缩水甘油醚混合。反应混合物在反应器中在55℃下搅拌6小时。接着,转移到玻璃吸滤瓶上并且以2柱容异丙醇、3柱容0.5M TFA溶液、2柱容水、4柱容1M氢氧化钠溶液并且接着以8柱容水洗脱。
分析:通过滴定确定的氨基浓度为265μmol/mL。
Claims (11)
1.吸附剂,用于从pH ≤ 5的溶液中结合金属,该吸附剂包括以含有一氨基的聚合物涂覆的多孔的支承材料,其中, 基于吸附剂的总体积,通过滴定确定的吸附剂的氨基的浓度至少是600μmol/mL;
其中,所述多孔的支承材料包括有机聚合物或者由有机聚合物与无机材料组成的复合材料;
其中,含有氨基的聚合物是聚烷基胺;
其中,含有氨基的聚合物是一交联的聚合物,并且含有氨基的聚合物与多孔的支承材料非共价地连接。
2.根据权利要求1所述的吸附剂,其中,含有氨基的聚合物的质量与多孔的支承材料的孔的总体积的比例大于或者等于0.1g/ml。
3.根据权利要求1或2所述的吸附剂,其中,基于多孔的支承材料的总体积,所述多孔的支承材料的孔体积处于30至90Vol.%的范围内。
4.根据权利要求1或2所述的吸附剂,其中,所述多孔的支承材料具有在6nm至400nm的范围内的平均的孔大小。
5.用于生产根据权利要求1所述的吸附剂的方法,所述吸附剂用于从溶液中结合金属,所述方法包括以下步骤:
(a)提供多孔的支承材料,该多孔的支承材料包括有机聚合物或者由有机聚合物与无机材料组成的复合材料;
(b)将含有氨基的聚合物通过孔填充方法施涂到多孔的支承材料上;
(c)去除在孔填充方法中使用的溶剂;
(d)重复步骤(b)和(c),以及
(e)交联含有氨基的聚合物。
6.根据权利要求5所述的方法,其中,步骤(b)和(c)在步骤(e)之前这样多次重复,使得基于吸附剂的总体积,在步骤(e)之后通过滴定确定的吸附剂的氨基的浓度至少是600μmol/mL。
7.根据权利要求5或6所述的方法,其中,含有氨基的聚合物的质量与多孔的支承材料的孔的总体积的比例在步骤(d)之后大于或者等于0.1g/ml。
8.根据权利要求5或6所述的方法,其中,在温度处于40至80℃ 的范围内下和/或在压力处于0.01巴至1巴的范围内实施步骤(c)。
9.根据权利要求5或6所述的方法,其中,在步骤(b)中含有氨基的聚合物在用于孔填充方法的溶液中的浓度处于5g/L至200g/L的范围内。
10.根据权利要求5或6所述的方法,其中,所述方法还包括步骤(f),有机残留物结合到含有氨基的聚合物上,所述有机残留物具有路易斯碱的特性。
11.吸附剂,所述吸附剂根据权利要求5至10中任一项所述的方法获得。
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JP7168181B2 (ja) * | 2017-12-27 | 2022-11-09 | ハイモ株式会社 | 金の回収方法及び金回収設備 |
DE202018100396U1 (de) | 2018-01-24 | 2018-02-19 | Instraction Gmbh | Vorrichtung zur Reinigung von Trinkwasser |
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CN111250047A (zh) * | 2020-01-21 | 2020-06-09 | 北京工业大学 | 一种重金属离子吸附剂及其制备方法与应用 |
CN112573612B (zh) * | 2020-11-30 | 2022-11-15 | 天津科技大学 | 一种利用亚胺型共价有机框架同时吸附苏丹红i-iv的方法和应用 |
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