CN106809906A - 水净化滤筒 - Google Patents
水净化滤筒 Download PDFInfo
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- CN106809906A CN106809906A CN201610818279.3A CN201610818279A CN106809906A CN 106809906 A CN106809906 A CN 106809906A CN 201610818279 A CN201610818279 A CN 201610818279A CN 106809906 A CN106809906 A CN 106809906A
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- filter cylinder
- polymer
- bed
- porous
- solution
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Abstract
本发明涉及包括交联聚合物或复合材料多孔粒子的滤筒,能够从饮用水和工业用水中高效能地去除溶解的有毒重金属离子。
Description
技术领域
本发明涉及包括交联聚合物或复合材料多孔粒子的滤筒,能够从饮用水和工业用水中高效能地去除溶解的有毒重金属离子和其他有害物质。
背景技术
从例如电镀车间中的工业废水、石化或制药行业的催化剂残留物、例如矿井的排放水和渗透水中去除或提取或回收含金属离子尤其是含重金属离子以及重金属污染土壤的复原成为日益重要的问题,因为含重金属离子特别是任何一种都对环境具有有害影响,并且在稀有或经济战略金属情况下,它们的回收具有经济利益。也就是说,一方面环保处于最前沿,另一方面贵重金属供给具有大的利益,贵重金属的可得性正日益变得有问题或者其价格正在上涨。去除或提取或回收含金属离子或含重金属离子的吸附剂的更重要的应用领域为它们在饮用水处理和海水淡化中的分离。同样地,例如用于氯碱电解或相似过程的浓盐溶液中含重金属离子的分离也具有大的利益。
现有技术中,过滤***用于例如使用吸附材料结合金属离子。然而,之前使用的***经常对某些金属离子表现出过低的选择能力或导致不需要的金属离子的不完全分离。在饮用水处理中,作为软化的副作用,经常存在非期望的淡化,由此钠离子含量大大上升。已知过滤***的进一步缺点为过低的效能或操作周期期间效能的下降。经常需要在高压下操作以增加效能。并且经常存在膜堵塞,例如在顺流反渗透中。另外,不需要的离子很经常地被释放进溶液。
因此本发明的目的是消除上述问题。
发明内容
通过水净化滤筒解决该问题,所述滤筒具有带有至少一个进水口102的筒上部101、带有至少一个出水口113的筒下部110以及围壁11,其中筒下部110和/或筒上部101是可移动的,其中所述滤筒内部具有一床,所述床包括平均粒径大于50μm到1000μm的含羟基或氨基基团的交联聚合物多孔粒子,其中所述床体积与所述床正面面积的比在大约0.03到大约1.5的范围内。
根据一实施例,所述床体积与所述床正面面积的比在大约0.1到大约1.0的范围内。这尤其涉及到将所述床在流动方向上布置为径向可灌注的布置中。在这之中,从顶部到底部将含金属离子溶液通过所述床。
根据进一步的实施例,所述床体积与所述床正面面积的比在大约0.03到大约0.05的范围内。这尤其涉及到所述床在流动方向上配置为径向可灌注的布置中。这样,从上方或底下将含金属离子溶液引进所述滤筒,接着径向通过所述床。
优选地,在流动方向上将多孔渗透膜或熔块布置在所述床上侧和/或所述床下侧。所述膜或熔块用于将粗颗粒过滤出溶液。
优选地,多孔渗透膜或熔块具有直径从5到50μm的小孔,优选地20到50μm。
在根据本发明的滤筒中,一方面能够将所述床布置为垂直或者径向可灌注。在所述垂直可灌注布置中,从上方或底下将含金属离子溶液通过所述床。在径向可灌注布置中,将含金属离子溶液径向通过所述床。在该布置中,所述正面面积与垂直可灌注布置相比增加。因此,改良筒几何形状、所述床的长度和直径变化是可能的。
优选地,所述滤筒中床的长度在1cm到50cm的范围内变化,更优选地,1到30cm。所述滤筒的优选直径在1到20cm的范围内,更优选地3到20cm,最优选地4.5到9cm。对于工业应用,所述床长度和床直径能够显著更大并在米范围中。
优选的床体积为50到1500cm3,更优选地,60到1400cm3,最优选地90到1325cm3。相应地,在工业应用中,所述床体积也增加。
优选实施例具有对圆柱筒来说的3.75cm半径、30cm床深度、44.2cm2正面面积和1325.4cm3床体积。
进一步优选实施例具有对圆柱筒来说的4.5cm半径、1到9cm床深度以及63.6cm2正面面积,优选地4.5cm床深度。
如上已经所述,所述滤筒包括一床,所述床包括多孔粒子,其中所述多孔粒子具有从100%干燥粒子开始的在水中300%的最大膨胀系数。
优选地,所述多孔粒子具有20-2000μm的平均粒径,优选地50-1000μm,最优选地80-500μm。进一步地,也能够包括一种移除微量污染物的材料,优选地活性碳。
根据所述滤筒的实施例,所述多孔粒子和所述移除微量污染物的材料布置在所述滤筒内的不同区域中。
根据进一步实施例,所述多孔粒子和所述移除微量污染物的材料存在于所述滤筒内的混合物中。
优选地,所述多孔粒子的干容重在0.25g/ml到0.8g/ml的范围内。
优选地,所述含羟基或氨基基团的交联聚合物在其侧链基团中被衍生化。
此外,基于聚合物中可交联基团的总数,所述含羟基或氨基基团的交联聚合物具有至少10%的交联度。
优选地,采用反向尺寸排阻色谱法测定,所述多孔粒子的平均孔径在1nm到100nm的范围内。
本发明的进一步主题为上述滤筒用于移除水中金属和重金属的用途。
此外,本发明的进一步主题为用于移除水中金属和重金属的方法,其中,如上所述,将所述水通过滤筒。
除了所述滤筒的特别几何尺寸以及就多孔粒子的床的直径、体积、正面面积和长度而言的比,多孔粒子材料的选择也是重要的。根据本发明,所述多孔粒子是为了用作色谱相或吸附剂。
然而,之前已知的相/吸附剂对所述应用领域来说经常没有足够的结合能力从而以足够程度结合到待结合的含金属离子,例如高浓度或低浓度溶液或强酸溶液,并且尤其在碱金属或碱土金属离子存在时。这尤其用于离子交换树脂。这经常由于这样的事实:含金属离子的结合位置不是适量存在,或者吸附剂没有足够选择性,以从重金属中区别碱金属和碱土金属。进一步地,之前已知的相在整个pH 0到pH 14的范围上经常不表现稳定性。这尤其用于基于硅胶的吸附剂。许多之前已知的相的进一步缺点为:尽管能够结合所需含金属离子,但是其不能从在单一方式或所有方式下使用的吸附剂中回收。由于已知吸附剂/相的结合能力通常不能令人满意,经常需要高的吸附剂体积/相体积,其结果是含金属离子的结合过程非常耗时费力和成本效率低。并且,由于含金属离子的已知结合吸附剂的通常低结合能力,需要更频繁再生或替换吸附剂。
这对用作分离的层析材料的吸附剂来说是同样真实的。此处经常使用由多孔载体材料和沉积其上的选择性结合复合物涂层组成的吸附剂。通常限制该吸附剂的结合能力,因为只能够用选择性结合复合物涂层载体材料的孔隙体积的一定比,从而仍然保持固定相的可利用度。另外,也存在所述载体材料与涂层以及靶分子的相互作用。这些相互作用导致更低的结合能力,并对某些色谱(过滤器)应用会非常有问题。因此,希望提供一种不存在这些所述缺点并且提高结合能力的色谱吸附剂。
因此,需要提供具有部分或完全没有上述缺点并在出口上的合适吸附剂的滤筒。
此外,与现有技术已知的金属结合吸附剂或色谱吸附剂比较,应该减小用于结合靶分子的所述吸附剂的体积,从而能够提供尽可能经济的滤筒。
根据本发明的例如用在滤筒中的交联聚合物多孔粒子的制备通常包括以下步骤:
(a)将有机聚合物以粒子形式用在多孔无机或有机载体材料上;
(b)在无机或有机载体材料的孔中交联有机聚合物;以及
(c)溶解出无机载体材料,获得交联聚合物多孔粒子。
以下将步骤(a)使用的有机聚合物只称为“聚合物”。
根据本发明,也能够将交联聚合物多孔粒子称为上述意义中的吸附剂。
优选地,粒子形式的多孔无机载体材料为中孔或大孔载体材料。多孔载体材料的平均孔径大小在6nm到400nm的范围内,更优选地,在8到300nm的范围内,最优选地在10到150nm的范围内。此外,优选地,多孔载体材料具有30vol.%到90vol.%范围的孔体积,更优选地40到80vol.%,最优选地60到70vol.%,在每种情况下基于多孔载体材料的总体积。根据DIN66133通过汞孔填充方法能够测定多孔载体材料的平均孔径大小和孔体积。
多孔无机材料为能够在优选地pH大于10的含水碱性条件下溶解的材料,更优选地pH大于11,最优选地pH大于12。也就是说,获得交联聚合物多孔粒子的将无机载体材料溶解出来的步骤(c)在所述含水碱性条件下发生。优选地,所述多孔无机材料为基于二氧化硅或硅胶或由其组成的材料。
优选地,所述有机多孔载体材料为选择***联有机聚合物,例如聚酯纤维。有机多孔载体材料溶出与正交吸附剂一起发生或在正交条件下发生。
所述多孔无机载体材料为颗粒材料,具有优选地20μm到2000μm范围的平均粒径,更优选地50μm到1000μm范围的平均粒径,最优选地80到500μm范围的平均粒径。此处颗粒形状能够为球状(球形)、杆状、双凸透镜状、多纳圈状、椭圆或者甚至不规则,优选地球形颗粒。
步骤(a)中使用的聚合物比例在5wt.%到50wt.%的范围内,更优选地10wt.%到45wt.%,仍然更优选地20wt.%到40wt.%,在每种情况下基于没有聚合物的多孔无机载体材料的重量。
根据本发明方法的步骤(a)中以粒子形式的多孔无机或有机载体材料上聚合物的应用能够通过各种方法实现,例如浸渍法或孔隙填充法,优选地孔隙填充法。与传统浸渍法相比,孔隙填充法具有有这样的优点,在一步骤中能够将全部的更大量溶解聚合物应用到多孔无机载体材料上,其结果为增加了结合能力。
在所有可能的方法中,步骤(a)中聚合物必须在溶剂中以溶解方式存在。随着应用在步骤(a)中的聚合物的溶剂,优选地使用在溶剂中可溶解的聚合物。应用在多孔无机或有机载体材料上的聚合物浓度优选地在5g/l到200g/l的范围内,更优选地在10g/l到180g/l的范围内,最优选地在30g/l到160g/l的范围内。
一般将孔隙填充法理解为一种以对应于多孔载体材料的孔的总体积的分量将包括待应用聚合物的溶液用在多孔无机或有机载体材料上的特定的涂覆方法。能够通过多孔无机或有机载体材料的溶剂吸收能力(WAC)测定多孔无机或有机载体材料的孔的总体积[V]。同样地,也能够测定相对孔体积[vol.%]。这是每种情况下载体材料自由开放孔的体积,因为只有这能够通过溶剂吸收能力测定。溶剂吸收能力说明需要什么体积的溶剂以完全填充一克干燥吸附剂的孔隙度(优选地固定相)。作为此处的溶剂,能够使用纯净水或水介质以及例如二甲基甲酰胺的有机溶剂。如果溶剂变湿时增加了它的体积(膨胀),那么自动包括为此耗费的溶剂的数量。对于WAC测量来说,将精确称量数量下的多孔无机载体与过量充分湿润的溶剂一起完全变湿,并且在离心机上通过旋转从空隙体积中移除过量溶剂。吸附剂孔内的溶剂由于毛细力保持在孔中。通过称量测定保留的溶剂质量并通过溶剂的密度将其转换为体积。吸附剂的WAC报告为每克体积干吸附剂(ml/g)。
在步骤(a)后而优选地步骤(b)前,通过优选地在40℃到100℃范围内的温度干燥材料以移除将聚合物应用在多孔无机或有机载体材料上的溶剂,更优选地在50℃到90℃范围内,最优选地在50℃到75℃范围内。此处特别地在0.01到1bar范围内的压力下进行干燥,更优选地在0.01到0.5bar范围内的压力下。
在步骤(b)聚合物交联之前能够一次或多次重复根据孔隙填充法和随后的干燥步骤的以粒子形式的在多孔无机或有机载体材料上的聚合物的应用的所述步骤(a)。如果在重复步骤中再次使用孔隙填充法,那么通过步骤(a)后的湿润和干燥材料的不同重量测定可用于多孔无机或有机载体材料上聚合物重复应用的孔的总体积。
优选地,通过在犁铧干燥机上干燥实现孔隙填充法中使用的溶剂的各自移除,因为该步骤能够产生明显的加速。
另外为了聚合物的重复应用,在步骤(a)后或步骤(b)后能够进行通过具有至少两氨基基团的有机化合物和能够进入具有所述氨基基团的至少两氮原子的共价键内的有机化合物的缩合反应应用聚合物的附加层的步骤。所述具有至少两氨基基团的有机化合物为包括达到氮和碳的比(N/C)优选地在0.1到1.1范围内的程度的氨基基团的有机化合物,更优选地0.4到1的范围内。所述具有至少两氨基基团的有机化合物能够为二胺、三胺、四胺或任一多胺。这方面的一示例为乙二胺。能够进入具有所述氨基基团的至少两氮原子的共价键内的有机化合物能够为例如以下进一步提及的与有机聚合物交联的交联剂。特别地优选地,此处使用表氯醇。
在多孔无机或有机载体材料上聚合物应用的步骤后或所应用聚合物的干燥后,在步骤(b)中实现无机或有机载体材料的孔中聚合物的交联。
基于聚合物可交联基团的总数,优选地,实现根据本发明方法的步骤(b)中无机或有机载体材料的孔中聚合物的交联,从而聚合物的交联度为至少10%。通过交联剂的相关需求量能够调整交联度。假设100mol.%的交联剂起作用并形成交联。这能够通过例如MAS-NMR光谱学和相对于使用的聚合物的量的交联剂的量的定量测定的分析方法验证。根据本发明该方法为优选的。然而,也能够通过基于例如使用率定曲线的C-O-C或OH振动的IR光谱学测定交联度。对本领域技术人员来说两种方法均为分析的标准方法。最大交联度优选地在60%,更优选地50%,最优选地40%。如果交联度超过规定上限,那么含氨基基团聚合物的聚合物涂层没有足够弹性并导致较低的含金属离子的结合能力。如果交联度低于规定下限,那么由此制备的交联聚合物多孔粒子没有足够刚性,例如用作色谱相的粒子,其中有时也应用高压。如果制备的交联聚合物多孔粒子直接作为色谱相的材料使用,那么聚合物的交联度优选地为至少20%。
用于交联的交联剂优选地具有两个、三个或多个官能团,通过其到聚合物的结合进行交联。用于应用在步骤(a)的聚合物交联的交联剂优选地从由二羧酸、三羧酸、尿素、双环氧化物或三环氧化物、二异氰酸酯或三异氰酸酯、二卤代烷或三卤代烷和卤代环氧化物组成的组合中选择,优选地二羧酸、双环氧化物和卤代环氧化物,例如对苯二甲酸、联苯二甲酸、乙二醇二缩水甘油醚、1,12-双(5-降冰片烯-2,3-二甲酰亚胺)癸烷-二羧酸和表氯醇,更优选地乙二醇二缩水甘油醚、1,12-双(5-降冰片烯-2,3-二甲酰亚胺)癸烷-二羧酸和表氯醇。在本发明的一实施例中,交联剂优选地为具有3和20原子之间长度的直线型分子。
步骤(a)中使用的聚合物优选地为包括羟基或氨基基团的聚合物,并且实际上优选地每个重复单元一羟基基团或氨基基团。将重复单元理解为沿着聚合物链以有规律的间隔重复的聚合物的最小单元。这样一种含羟基聚合物的示例为聚乙烯醇。含氨基基团聚合物优选地为具有主要和/或次要氨基基团的聚合物。虽然其能够为同一重复单元的聚合物,但是其也能够为优选地具有单一烯烃单体或例如作为共聚单体的乙烯吡咯烷酮的的两极惰性单体的共聚物。
以下为含氨基基团聚合物的实施例:多胺,例如任何聚烷基胺,例如聚乙烯胺、聚烷基胺、聚乙烯亚胺和聚赖氨酸等等。在这些之中,优选地聚烷基胺,仍然更优选地聚乙烯胺和聚烷基胺,特别优选地聚烷基胺。
根据本发明方法的步骤(a)中使用的聚合物的优选分子量优选地在5000到50000g/mol的范围内,其尤其用于所述聚乙烯胺。
将步骤(c)中无机载体材料的溶出理解为将无机载体材料从步骤(b)后获得的多孔无机或有机载体材料的复合颗粒和所用聚合物中移除。优选地在pH大于10的碱性水溶液中实现步骤(c)的获得交联聚合物多孔粒子的溶出无机载体材料,更优选地pH大于11,仍然更优选地pH大于12。作为此处的碱,优选地使用金属类氢氧化物,更优选地氢氧化钾或氢氧化钠,进一步更优选地氢氧化钠。基于溶液的总重,此处最好为水溶液中碱金属类氢氧化物的浓度为至少10wt.%,仍然更优选地25wt.%。在这之中,根据本发明方法的步骤(c)中,将步骤(b)中获得的粒子与相关碱性水溶液接触几个小时。接下来,从与水一起的交联聚合物多孔粒子中洗出溶解的无机载体材料,直到产物中基本不再包括无机载体材料。这具有这样的优点,在根据本发明生产的交联聚合物多孔粒子的使用中,例如作为金属的结合材料,现在这只由有机材料组成并因此能够完全焚烧而没有金属残留和还原残渣。
此外,能够在步骤(c)后在交联聚合物的侧链基因上衍生交联聚合物。在这之中,优选地将有机残留物结合到聚合物。该残留物能够为任何可能的残留物,例如脂族和芳香族基团,其也能够具有杂原子。也能够将这些基团替换为阴离子或阳离子残留物或可质子化的或不可质子化的残留物。如果将根据本发明方法获得的交联多孔聚合物用于从溶液中结合金属,那么将聚合物的侧链基团衍生所得的原子团为具有路易斯碱性能的原子团。将具有路易斯碱性能的有机残留物理解为尤其与待结合金属形成复杂键合的残留物。包括路易斯碱的有机残留物为例如那些具有杂原子的有机残留物,所述杂原子具有自由电子对,例如N、O、P、As或S。
优选地,聚合物衍生的有机残留物为以下所示的配体
尤其优选地为配体PVA,也就是PVA、NTA、EtSH、MeSH、EDTA和iNic或上述组合。例如,尤其优选地为PVA与NTA或EtSH的组合。
尤其优选地,将聚乙烯胺用作所述方法中的聚合物,因为聚乙烯胺的氨基基团为其自身的路易斯碱并且通过其作为亲核基团的性能能够轻易地耦合到具有亲电中心的分子。优选地,此处使用形成次要氨基且不形成酰胺的耦合反应,因为经过次要酰胺的形成,在过程中不丢失路易斯碱度。
本发明也涉及通过上述方法获得的交联聚合物多孔粒子。此处优选地,根据本发明制备的粒子具有水中300%的最大膨胀系数,假设用于干燥粒子的值为100%。另一方面,根据本发明的粒子能够在水中最多增加三倍重量。
本申请的进一步主题也是交联聚合物或含氨基基团聚合物多孔粒子,其中这些粒子也具有300%的最大膨胀系数,假设干燥粒子的百分比为100%。也就是说,根据本发明的这些多孔粒子也能够具有在水中膨胀的最多三倍体积增加。
然而,进一步更优选地,上述方法制备的粒子或根据本发明的粒子具有水中250%的最大膨胀系数,进一步更优选地为200%,最优选地为150%,因为否则获得的粒子的刚度至少对压力下的色谱应用来说不够高。
上述方法制备的多孔粒子和多孔粒子自身优选地属于交联含氨基基团聚合物。优选地,含氨基基团聚合物或由其组成的多孔粒子具有由至少800μmol/ml滴定法测定的氨基基团浓度,更优选地至少1000μmol/ml,进一步更优选地至少1200μmol/ml。将滴定法测定的氨基基团浓度理解为根据本申请实施例部分说明的4-甲苯磺酸的穿透测量的分析方法获得的浓度。
因此,优选地,制备的粒子或根据本发明的粒子具有0.25g/ml到0.8g/ml范围内的干容重,进一步更优选地0.3g/ml到0.7g/ml。也就是说,作为整体的多孔粒子为极轻的粒子,其通过获得的高孔隙率确保。不管所述粒子的高孔隙率和轻重量,其具有相当高的机械强度或刚度并能够用作色谱应用中压力下的相。
反向尺寸排阻色谱法测定的根据本发明的多孔粒子或根据本发明制备的多孔粒子的平均孔径优选地在1nm到100nm的范围内,更优选地2nm到80nm。
因此制备的多孔粒子或根据本发明的多孔粒子优选地为具有与溶出多孔无机载体材料具有的粒子的形状相似的形状,但是附带条件为根据本发明的多孔粒子或根据本发明制备的多孔粒子基本反映它们的材料,即溶出多孔无机载体材料的孔隙***,也就是在根据本发明方法的步骤(b)中理想孔隙填充法的情况下,它们为所用的多孔无机载体材料的反向孔隙图像。根据本发明的多孔粒子或根据本发明制备的多孔粒子形状上优选地为基本球形。它们的平均粒径优选地在5μm到1000μm的范围内,更优选地在20μm到500μm的范围内。
此外,根据本发明的交联聚合物多孔粒子或根据本发明制备的交联聚合物多孔粒子的特征在于它们基本由交联聚合物组成。在这种情况下,“基本”意味着多孔粒子中进一步能够包括例如无机载体材料的仅仅不可避免的残留物,然而,其含量优选地低于2000ppm,进一步更优选地1000ppm,最优选地500ppm。也就是说,优选地,根据本发明的交联聚合物多孔粒子或根据本发明可制备的交联聚合物多孔粒子基本不受无机材料的影响,例如无机载体材料的材料。这也意味着上述与根据本发明方法的步骤(c)相关的当其说明产物中基本不再包括无机载体材料。
本发明也涉及复合材料,其中根据本发明的多孔粒子或根据本发明制备的多孔粒子存在为以连续水相的形式散开,其中将所述连续水相嵌入水凝胶和/或为水凝胶的组成部分和/或由不溶于水的离子可渗透涂层包围所述连续水相。
优选地呈现根据本发明的复合材料,从而根据本发明的多孔粒子或根据本发明制备的多孔粒子以嵌入在水凝胶中的连续水相存在。
此处将水凝胶理解为含溶剂的(优选地,水)然而为可溶溶剂的聚合物,其分子以例如共价键或离子键的化学方法或例如聚合物链纠缠的物理方法链接到三维网络。由于内置的两极(优选地,亲水的)聚合物组成部分,它们在溶剂中(优选地,水)膨胀,伴随着显著的体积增加,而不会失去它们的材料凝聚性。
优选地,根据本发明的复合材料以能够为球状、双凸透镜状或杆状的粒子形式存在,优选地为双凸透镜状粒子。优选地,所述双凸透镜状粒子具有1mm到10mm范围内的平均宽直径和100μm到1000μm范围内平均高度。
包括根据本发明的多孔粒子或根据本发明制备的多孔粒子的连续水相的水凝胶能够为任何可能的水凝胶,优选地基于有机聚合物的水凝胶。形成水凝胶的有机聚合物优选地为具有大量羟基的有机聚合物。在本发明的非常特殊的实施例中,所述水凝胶由基于聚乙烯醇的聚合物形成。
优选地,由包括以下步骤的方法制备所述复合材料:
(a)制备包括能够形成水凝胶和添加剂的水溶液;
(b)将根据本发明的多孔粒子或根据本发明制备的多孔粒子添加到所述水溶液;
(c)从步骤(b)的水溶液中的水的移除至多50wt.%含水量,其基于水移除后水溶液的总量,由此相位分离发生在包括所述添加剂的水相和以水凝胶的形式包括能够形成水凝胶的聚合物的相中,其中所述水凝胶包括所述多孔粒子;以及
(d)获得复合材料的两相的分离。
所述能够形成水凝胶的聚合物优选地为包括大量羟基的有机聚合物。此处,特别优选地使用聚乙烯醇。
步骤(a)水溶液中能够形成水凝胶的聚合物的浓度优选地在4到30wt.%的范围内,更优选地6到16wt.%,其基于水溶液的总重。
步骤(a)中使用的添加剂优选地为亲水性至少比得上能够形成水凝胶的聚合物的亲水性的添加剂。根据本发明方法的步骤(a)中使用的添加剂的示例为纤维素酯、纤维素醚、淀粉酯、淀粉醚、聚亚烷基二醇醚、聚二醇、长链醇(n>8)、糖酯和糖醚,优选地作为添加剂的聚二醇。
根据本发明方法的步骤(a)中使用的添加剂优选地在4到20wt.%的范围内的浓度下使用,更优选地6到10wt.%,其基于水溶液的总重。
在优选改进中,也能够执行水移除(步骤c)一直到残留含水量为10到30wt.%。优选地,在将溶液倒入优选地精确包括待获得复合材料的所需形状的模具后进行水溶液中水的移除。
在步骤(d)的两相分离后,获得接着优选地在自来水或盐溶液中再水合的复合材料。
另外,作为根据本发明的用于制备复合材料的所述方法的替换,其也能够由具有以下步骤的替换方法制备:
(a)将根据本发明的多孔粒子或根据本发明制备的多孔粒子分散在包括交联剂、交联剂可交联水凝胶的前驱体或水凝胶的热可交联前驱体的水相中,获得分散体;
(b)从(a)中获得的分散体形成复合材料,其中
(b1)为获得与基本不溶于水的离子可渗透涂层的封装,将包括交联剂的分散体引入包括交联剂可交联的不溶于水的离子可渗透涂层的凝胶前驱体的溶液中,或
(b2)为形成离散凝胶粒子,将包括通过热或冷的热可交联的水凝胶的前驱体的分散体引入对于凝胶前驱体的热交联来说具有足够高温或低温的水相,或者
(b3)将包括交联剂可交联的凝胶的前驱体的分散体引入包括所述交联剂的溶液中或者将所述交联剂并入所述分散体中。
本发明的进一步实施例涉及根据本发明的多孔粒子或根据本发明制备的多孔粒子和根据本发明的复合材料用于有机分子的提纯或溶液中含金属离子的分离。在这之中,根据本发明的多孔粒子或根据本发明制备的多孔粒子优选地用在允许有机分子的提纯或溶液中含金属离子的分离的色谱法,更优选地有机分子的提纯。优选地,根据本发明的复合材料用于溶液中含金属离子的分离并能够例如以简单方式用在搅拌容器或仅仅将所述复合材料加到含金属溶液并搅拌一定时间而由此含金属粒子从复合材料的溶液中分离的“流化床”应用中。
进一步地,根据本发明的使用中,优选地,完全由有机材料或多孔材料组成的复合材料用于结合金属后能够进行焚烧而没有金属回收的残留物,其结果是金属能够以这种方式回收。
也就是说,因此本发明也涉及有机分子的提纯或溶液中含金属离子的分离的方法,其中,溶液与根据本发明的多孔粒子或根据本发明制备的多孔粒子或根据本发明的复合材料接触。
根据本发明含金属粒子将被结合的溶液能够被浓缩或稀释含水、非水、酸性、碱性或中性溶液。
根据本发明的将从这些溶液中获得或结合的含金属离子优选地为以离子形式(金属离子)存在在所述溶液中或也以离子形式作为金属配体配位化合物存在的金属。优选地,所述金属为复合成形金属,也就是能够进入金属配体配位键的金属。更优选地所述金属为过渡金属或稀土金属,进一步更优选地为贵金属或稀土金属。相当优选地为金属铜、镍和铬。
根据本发明使用的进一步实施例中,含金属粒子将被结合的溶液为具有至少5g/l碱离子含盐量的溶液。
此外,含金属粒子将被结合的溶液优选地为水溶液,尤其是酸性水溶液,其pH≤5,更优选地≤4,进一步更优选地≤3。
本发明也涉及滤筒,例如用于饮用水处理,其包括根据本发明的交联聚合物的多孔粒子或根据本发明的复合材料。优选地,饮用水的处理应该在pH范围6.5-9.5中实现。所述滤筒优选地成形为使待处理的饮用水能够通过所述筒并在其内部与根据本发明的交联聚合物多孔粒子或根据本发明的复合材料接触,由此将含金属离子从水中移除。
另外,所述滤筒能够包括移除微量污染物的材料。对于此,优选地使用活性碳。能够将各种材料布置在所述滤筒内的分离区域中或两材料的混合物中。
所述滤筒能够以所有可能规格配置。例如所述滤筒能够以满足家庭中日常饮用水需求的规格配置。然而,所述滤筒也能够具有使其可以覆盖多个家庭饮用水需求的规格,也就是例如超过5升每天的需求。此外,在开头时说明了关于直径/半径、床深度、正面面积和床体积的优选规格信息应用。
为了也像含金属离子和微量污染物那样从水中移除悬浮物质,所述滤筒也能够包括过滤悬浮物质的薄膜。
现在根据以下附图和实施例说明本发明,然而,其仅仅作为示例的方式:
附图说明
图1示出了根据本发明的交联聚合物多孔粒子的照片;
图2示出了作为溶液中Cu2+浓度的函数的Cu2+的结合量的等温线;
图3-10示出了应用实验的测量结果;
图11示出了VariPrep D44类型的空筒和装有50μmMetCap T的筒的压力降;
图12-17示出了MetCap T筒的穿透曲线;
图18示出了根据本发明的滤筒;
图19示出了空滤筒的压力降;
图20示出了装满了的滤筒的压力降(关于颗粒大小的不同相的两不同筒设计);
图21示出了根据本发明的作为流速函数的滤筒的进一步实施例的穿透曲线;
图22示出了根据本发明的滤筒的进一步实施例的铜穿透曲线(饮用水中2000ppm)(300x 75mm i.d.深床筒);
图23用图解法示出了滤筒结构。
具体实施方式
分析方法:
利用4-甲苯磺酸的穿透性测量的吸附剂的氨基浓度的测定(滴定分析):
用待测试的固定相的柱测定动态阴离子置换能力。为此,首先以三氟乙酸置换所述柱中的所有可置换阴离子。接着用4-甲苯磺酸含水试剂溶液冲洗所述柱,直到该溶液在所述柱的末端以相同浓度再次出现(穿透)。从4-甲苯磺酸溶液的浓度、流速和色层谱中穿透的面积计算由所述柱结合的4-甲苯磺酸溶液的量。因此,测定的4-甲苯磺酸溶液的量给出吸附剂的氨基浓度。
水中4-甲苯磺酸的动态阴离子置换能力为基于相体积并以每升毫摩尔报告(mM/l)。
实施例1:根据本发明的交联聚合物多孔粒子的制备:
首先,以下用聚乙烯胺数次涂层硅胶载体:
第一次涂层
将5000g硅胶M.S Gel D50-120A(WAC 1.08ml/g)装进VT20犁铧混合机的20L转鼓。并行制备聚乙烯胺聚合物溶液。为此,称量4946g的10.1%含水聚乙烯胺溶液(PVA溶液)。通过添加245g32%的盐酸将聚合物溶液的pH调整到9.5。接下来加入243g水。将该PVA溶液在30分钟内慢慢加到混合转鼓中的硅胶(混合器转速为120RPM)。接下来,将被涂层的硅胶进一步混合30分钟。将被涂层的聚合物被吸附物在室温下储存24小时。将犁铧混合机的转鼓加热到60℃。接下来,将溶剂移除并将产物在30mBar的干燥机中干燥到固定重量。产出5573g聚合物被吸附物。
第二次涂层
在VT20犁铧混合机的混合转鼓中第二次涂层干燥的聚合物被吸附物(5573g)。对于覆盖的所述聚合物溶液的制备,称量3956g12.6%的PVA溶液并通过添加278g32%的盐酸将溶液的pH调整到9.5。接下来加入704g水。在用蠕动泵的犁铧混合机的转鼓中(转速120rpm)以计量的方式在30分钟内将涂层溶液送进聚合物被吸附物。将聚合物被吸附物混合30分钟,接着储存24小时。将犁铧混合机的转鼓加热到60℃。在减压(30-50mBar)下的干燥机中将湿润的聚合物被吸附物干燥到恒重。产出6115g聚合物被吸附物。
第三次涂层
在VT20犁铧混合机的混合转鼓中再一次涂层干燥的聚合物被吸附物(6115g)。对于涂层的聚合物溶液的制造,称量3967g 12.6%的PVA聚合物溶液并通过添加264g 32%的盐酸将溶液的pH调整到9.5。接下来加入204g水。在用蠕动泵的犁铧混合机的转鼓中(转速120rpm)以计量的方式在30分钟内将涂层溶液送进聚合物被吸附物。将聚合物被吸附物混合30分钟,接着储存24小时。将犁铧混合机的转鼓加热到60℃。在减压(30-50mBar)下的干燥机中将湿润的聚合物被吸附物干燥到恒重。产出6670g聚合物被吸附物。
聚合物的交联和载体的溶解:
称量500g聚合物被吸附物到2L烧瓶内。接下来,加入溶解在200ml二甲基甲醇中的129g环氧氯丙烷,并将粉末在60℃下混合24小时。接下来加入1L 25%的氢氧化钠溶液,并将悬浮液混合4小时。在具有以下溶剂的过滤器熔块上洗涤获得的悬浮液:
2L 1M氢氧化钠溶液、2L去离子水、2L 2M水中的盐酸、2L去离子水、4L 1M氢氧化钠溶液和4L水。
产出:1L模板相(MetCap T相,PVA相)
阴离子产量:1808mM/ml
图1示出了根据本发明的直径在10和50μm之间的粒子形式下的交联多孔聚合物的照片。
具有配体氨三乙酸(NTA)的模板基相的衍生反应
在使用2L DMF的玻璃过滤器熔块上用DMF冲洗300ml的模板相(实施例1)。接下来,在500ml DMF中悬浮原材料并将原材料转移进具有机械搅拌器的2L双夹套反应釜。称量143.35g氨三乙酸[139-13-9]Alfa Aesar产品编号A11936Lot.5001P11P并在500ml DMF中溶解。在第二个容器中,称量284.43g 2-(1H-苯并***类-1-基)-1,1,3,3-偶氮苯并三氮唑(HBTU)[94790-37-1](Iris BioTech GmbH Lot:20141120)并在500ml DMF中溶解。将两试剂溶液传递到搅拌相悬浮液内。接下来,也将105ml三乙胺[121-44-8](TEA)(Bernd KraftLot 1638629)直接传递到反应器内。将悬浮液加热到65℃6小时。接下来,将悬浮液从反应器传递到4L玻璃过滤器Nutsche(Por.4)上并以以下溶剂洗涤相:1L DMF、1L乙酸、1L 20%的含水乙醇溶液、1L 1M氢氧化钠溶液和1L 20%的含水乙醇溶液。
将相储存在20%的含水乙醇溶液中。
阴离子置换能力:TSS 1220μmol/ml
实施例2:根据本发明的复合材料的制备:
根据DE 198 27 552 C1制备包括根据实施例1的交联多孔聚合物的双凸透镜状凝胶体。
实施例3:根据本发明的复合材料用于从溶液中分离金属:
对于水溶液中Cu2+消耗,将根据实施例2的包括50mg双凸透镜状凝胶体的1ml溶液与2.5ml含水Cu2+溶液一起温育24小时。分离溶液的上层清液并用FAAS进行分析。表1示出了Cu2+的结合量。图2示出了作为溶液中Cu2+浓度函数的Cu2+结合量的吸附等温线;
表1:
应用实施例Al-All
实施例A1:在一个筒中的不同相类型的饮用水应用/组合
(来源:HV 16012)
对于饮用水净化来说,组合几种MetCap T相类型(至少为2)从而能够有效可靠地覆盖尽可能宽的重金属谱的范围。
实验:
将98mg CuSO4x 5H2O和101mg NiCl2x 6H2O加到50l自来水中并彻底混合,结果为每种情况下5ppm重金属结果的浓度。接着以45ml/min(2.7l/hr,10床体积/h)的流速输送溶液经过包括MetCap T氨基基相和MetCap T NTA相的筒(4.4x18cm,稍微圆锥状,体积:≈274ml)。分馏收集流出物。通过AAS或者Hach-Lange试管试验测试馏分的重金属。
Hach-Lange试验:
·铜,LCK529,0.01-1.0Cu
·镍,LCK537,0.05-1.0mg/l Ni
另外通过AAS测试铜。
图3和4示出了试验结果。
自来水中初始浓度为0.5ppm的铜和镍两者在整个观察范围都显着地减少,有时低于分析方法的检测极限。
实施例A2:在一个筒中的不同相类型的饮用水应用/组合
具有浓铜溶液的饮用水筒上的能力测定给出了每毫升非常高的承载能力以及在不同流速的函数。未观察到随着流速增加,能力减小。
实验:
以不同流速(10-100床体积每小时,BV/h)输送800ppm铜溶液(作为CuSO4x5H2O)经过包括MetCap T氨基基相和MetCap T NTA相的筒(4.4x18cm,稍微圆锥状,体积:≈274ml)。分馏收集流出物。通过AAS测试馏分中的铜。
图5示出了10-100床体积每小时(BV/h)的不同流速下流出物中铜浓度的发展。
两曲线在大约拐点的高度处交叉。这意味着承载能力不受流速影响。100BV/h流速的1%穿透稍微在10BV/h流速的1%穿透之前。对此而言动力学原因会是决定性的。虽然如此,***的绝对能力保持不受影响。
实施例A3:普遍性(PSE)
来源HV15091
MetCap T相-作为氨基相和衍生特殊相的特点在于应用的巨大范围:所有重金属能够形成化学络合物。MetCap T相给配体提供这些化学络合物并因此能够用于所有重金属。由于碱金属和碱土金属通常只形成非常弱的化学络合物,它们通常不被结合。到那时取决于离子交换剂的本质区别,其结合所有类型的带电粒种,因此选择性要低很多。
以下数据基于12种代表性重金属说明元素周期表中该类元素的无限范围应用。
实验:
称量各自相的100mg、与各自金属盐的5ml含水10ppm、100ppm和1000ppm溶液一起处理并在20℃下摇晃24小时。接下来,通过AAS测定上层清液重金属的浓度。
表2:
在大多数情况下AAS不再能够检测到上层清液中金属的残余浓度。只有对钯和锌来说,进一步发现低的残余浓度。MetCap T相示出了完全的结合,尤其对有价值的贵重金属金、银、铜、铅和铂,即使在1000ppm的供应浓度下。
来源:HV 16009
实验:
称量各自相的100mg、与各自金属盐的5ml含水10ppm和100ppm溶液一起处理并在20℃下摇晃24小时。接下来,通过AAS测定上层清液重金属的浓度。
表3:
TP214:MonoPlus TP214为具有硫脲基团的单粒度体系、大孔隙螯合树脂(制造商Lanxess):
BV 15069:MetCap T
表格示出了MetCap T相与来自竞争者的商业比较相之间的有毒重金属消耗的比较(在室温下保温)。
在任何情况下(除了汞以外,两相表现地非常好),有毒重金属的可测残留量在MetCap T相的情况下低于商业比较凝胶。
实施例4:高浓度镍动态结合
来源AL 16001
实验:
以1ml/min的流速输送500pm镍(pH4)的水溶液经过装有各自相的柱(33.5x 4mm)。在贯流分析池中以720nm测试流出物。测量结果见以下表4:
表4:
MetCap T相示出了镍容量比类似基于聚苯乙烯(PS)相高2-3倍。
实施例5:高浓度铜动态结合
HV15090:
具体特点:基相和衍生的制备方式对MetCap T相的结合性能具有显著的影响。
实验:
以1ml/min的流速输送800ppm铜(pH5)的水溶液经过装有各自相的筒(33.5x4mm)。在贯流分析池中以790nm测试流出物。
表5:
HV 15106:
具体特点:通过某些配体/结合基团的引进,水溶液的镍结合能力显着上升:
EtSH、NTA或者MeSHAr基团的衍生作用导致与未衍生化的PVA基相(BV 15068)相比承载能力分别增加到64%、81%和55%:
表6:
因此,应该将该工艺作为使得调整相性能为指定任务成为可能的平台技术:例如,如果从水溶液中结合镍,那么优选地为纯氨基基相的衍生相。
实施例A6:静态条件下含水有机溶液的钯结合
来源:HV 15097-与EP 14043Lewatit TP207(制造商:Lanxess;载体:聚苯乙烯;配体:亚氨基二乙酸)比较的动力学
具体特点:
由于它们的有利流动特性和最佳化扩散途径,MetCap T相的金属吸收发生地比传统材料快得多。
实验:
在每种情况下,与100mg相一起温育水/乙腈/异丙醇中的320ppm钯溶液9x。在10分钟、30分钟、1小时、2小时、3小时、4小时、5小时、6小时和24小时后移除上层清液并通过AAS测定钯浓度。
测试结果见图6。
BV15065 MetCap T氨基类型
EP14043 Lewatit TP207(亚氨基二乙酸)
大约10分钟后,在MetCap T温育系列的情况下钯浓度下降到初始值的大约50%。大约100分钟后,该系列中的溶度下降到AAS检测极限以下(检测限AAS 0.25ppm)。在竞争者相的情况下,溶度减小要慢得多(半衰期大约3小时),甚至在24小时后只到达高得多的值,其说明有限时间的不完全结合。
该结果示出了instrAction MetCap树脂的使用不局限于纯粹的水溶液***。
实施例A7:金属动态结合:铂、铅、铑
来源:HV15088:钯穿透
具体特点:
钯(pH1.1)的非常强的结合在很大程度上是可逆的。在这种方式下能够反复地使用该相。没有焚烧下钯的回收是可能的。由于非常强的结合,也能够有效和高收益(此处为100%)处理非常低浓度的溶液。
实验:
与MetCap T(分批处理BV 15047)一起包装规格30x 4.6mm的聚醚醚酮柱,并以1ml/min的流速将水(pH 1.1)中大约60ppm钯的溶液通过该柱。收集流出物并通过AAS对钯测试。结果见图7。
在大约350ml的整个穿透体积上,溶液中没发现钯(检测极限:AAS 5ppm)。因此,所述柱吸收大约35mg钯。这对应于>75mg钯/ml相。在该实验中未达到该相的吸收能力。
通过与50ml 1M HNO3一起洗脱,回收77%的结合钯。
铅穿透
来源:HV15088:
实验:
与MetCap T(分批处理BV15047)一起包装规格30x 4.6mm(0.5ml)的聚醚醚酮柱,并以1ml/min的流速将水(pH 5)中大约80ppm铅的溶液通过该柱。收集流出物并通过AAS对铅测试。结果见图8。
在第一大约110ml中,铅是不可测的(检测极限AAS:0.5ppm)。接着开始逐步穿透。只有在大约400ml(800床体积)后才达到大约80ppm的初始浓度。
不能从1M HNO3的相中洗脱结合铅。
因此,结果表明该技术不仅能用于过渡族元素和贵金属,也能用于所有能够络合物形成的元素。
铑穿透HV15088
与MetCap T(分批处理BV 15047)一起包装规格30x 4.6mm(0.5ml)的聚醚醚酮柱,并以1ml/min的流速将水(pH 5)中大约60ppm铑的溶液通过该柱。收集流出物并通过AAS对铑测试。结果见图9。
在第一大约110ml(220床体积)中,铑是不可测的(检测极限AAS:0.5ppm)。接着开始逐步穿透。在大约150ml(300床体积)后才达到大约60ppm的初始浓度。
不能从1M HNO3的相中洗脱铑。
实施例A8:搅拌容器级联中水溶液的银
来源:HV 15078
将5ml硝酸银水溶液(浓度74.2ppm)加到100mg单相并在20℃下进行24小时摇晃。接下来,移除上层清液,通过AAS测定银浓度。与100mg新相一起再次温育其余的上层清液。总共进行该过程四次(第一到第四级联)。以下表格汇总了AAS测量的结果:
表7:
表7示出了MetCap T相(最后一栏)是唯一一个能够在三个级联内完全将银消耗到低于AAS的检测界限(检测界限AAS 0.1ppm)的测试相。甚至在第二级联后结合>97%的银。此处可见MetCap T材料在基于聚苯乙烯相之上的优势:甚至35μm粒子(栏3和4)示出了比50μm MetCap T相更低的动力学和绝对能力。
实施例A9:以磷酸盐形式存在的铁或铝
来源:HV15094
在每种情况下,将5ml的含水10%磷酸溶液加到100mg单相并在20℃下摇晃24小时,该溶液之前已经用氢氧化钠溶液调整为pH 3并分别包括10和100ppm的铁或铝。接下来通过AAS测定上层清液中金属的浓度。
表8:
不考虑浓度,一步中含磷水溶液中铁的消耗完全低于检测极限(0.5ppm)。对于铝,一步中产生~80-90%的消耗。这证明在盐和例如磷酸配体的络合剂的存在下MetCap相的消耗能力。
实施例A10:含水、浓盐溶液中的锰、镍、铝(0-2M NaCl)
具体特点:
用MetCap相从浓盐溶液中移除极重要重金属是非常成功的。因此打开了宽广的应用领域,例如海水淡化或氯碱电解。在两种情况下,主要益处在于移除伤害两过程中使用的灵敏膜的重金属。
来源:HV 15095
实验
准备锰(10ppm)、铝(100ppm)和镍(10ppm)的三种溶液,每一种在0M、1M和2M NaCl溶液中(总共为9种溶液)。在每种情况下,与100mg MetCap T一起将5ml该溶液在20℃下摇晃24小时。接下来,分离上层清液并通过AAS测定上层清液的金属浓度。
表9:
锰 | 铝 | 镍 | |
[NaCl] | [ppm] | [ppm] | [ppm] |
初始浓度 | 10 | 100 | 10 |
0M | - | 2 | 0 |
1M | 0 | 5 | 0 |
2M | 0 | 14 | 0 |
表格示出了从溶液中完全移除锰和镍到低于AAS的检测极限(检测极限:锰:0.1ppm,镍:0.1ppm),不考虑它们的含盐量。铝的浓度显著减少了86-98%。
因此,MetCap T相结合重金属,不考虑它们的含盐量。在这些条件下例如铝的轻金属被结合86-98%。
实施例A11:再生性能
具体特点:
在大多数应用中,能够再次使用MetCap T相而能力不丢失并且不用对其他性能(例如背压力)进行选择或改变:
来源:HV 16025
以1ml/min的流速下输送500ppm镍(pH 4)的水溶液经过装有各自相的柱(33.5x4mm)。在贯流分析池中以720nm测试流出物。再生:80ml 0.5M HCl,接着用80ml 0.5M NaOH。
在图10中叠印了上述操作的三个穿透。
基于色层谱中的突出点(0%、50%和100%的穿透),见到再生相的不变能力和相同表现。在检测器上波动产生吸收的绝对高度。
实施例滤筒F1到F3
实施例F1:标准筒D44(几何级数定义)
通过根据本发明的平均粒径为50μm的交联聚乙烯胺球形树脂的准备,填充规格180x 44mm的筒(VarioPrep D44)。用于急骤层析或SPE中的该市售壳体被选择为填充性能和其生产率的第一阐释,并且具有轴向可压缩的大约180x 44mm床体积。用Luer-Lock技术制备入口和出口。通过具有7μm截止点的熔块所在的分配板上的大约1.5mm宽和大约1cm长的通道进行入口上的转移。50μm MetCap T的填充层连接到这上面。同样地,出口通过12μm截止点的熔块、分配板和通道产生Luer-Lock连接。为了测试压力流性能,因此在测定的筒入口上用不同体积流速和压力降的自来水操作定做的筒(见图11)。
之前以120CV/h的流速测定材料的化学适用性。因此,发现得到,对于饮用水基质中各种重金属离子的足够选择性来说,不得不在MetCap T载体上使用合适的配体。通过实施例的方式,此处会提及分别为MetCap T“NTA”和“EtSH”类型的配备有一级胺的MetCap T类型基相、配备有氨三乙酸基团的相和配备有乙硫醇的相的选择性。
虽然MetCap T能够从饮用水中结合铜离子,但是这只对较小范围的镍离子是可能的。该改良相的下行通道只提供于移除以及因此溶解镍的结合。层化引进该相到筒中从而确保待单独结合的重金属离子每一相类型的最大能力。图12到17示出了具有不同加载的镍和铜的各自的穿透曲线。
实施例F2:平台型筒45x 900mm
从上述结果中,看出溶解重金属的良好化学选择性伴随着显著能力以及因此从理论上讲对选定材料-筒组合的显著的可达到的使用寿命。然而,之前考虑的***的生产率被发现为低的非常令人不满意,大约1bar压力降只有2.75l/h。
因此,为了提高产量,发明第一流动-和床-最佳化筒类型。筒设计中的该改变侧面为对包装的MetCap T的粒径重叠。因此,下一步包括具有与原先体积相等的dP=100μm的275mlMetCap T填充的尺寸为45x 90mm i.d.的原型筒。
此处也为了检查生产率,在不同流速下测定压力流曲线。结果见图20。
令人惊讶地,同一压力降下能够获得从10到50CV/h(2.75到13.75l/hr)的五倍生产率增加(见图21)。令人惊讶地,尽管一般来说更少的有利流动几何特性,但是消耗非常好。同样应用到加载。没有观察到锥形流动特性。
为了测试化学功能,在10和100CV/h的流速和2000mg/1(pH=5)含水铜溶液下记录穿透。穿透轮廓透露重复加载和卸压周期之间的几乎不变的产量。然而,可视穿透侧面的倾斜度展平在100CV/hr流速下,导致伴随定量消耗的更低的流出物体积(见图22)。
实施例F3:300x 75mm i.d.的深床筒
进一步的实施例涉及可用床体积和传递通道、熔块和进料连接器的最优化。对此,制造300x 75mm i.d.(V=1.325L)类型的进一步的原型筒,其用100μm MetCap T填充。在该筒中,在6mm管径的G1/4"中实施连接器。并且,使用具有40μm截止点的熔块。图22示出了该规格的筒上的铜穿透(饮用水中2000ppm铜)。即使在该非常高浓度下,在第一25l中就将铜耗尽到低于AAS检测器的检测极限(0.1ppm)。
本发明的优势:
本发明使有毒重金属能够从饮用水中完全移除。该移除效果为至少50床体积/小时的高生产率。
本发明不需要泵和电能,而是只需要本发明几乎不削弱的现有主压力。
能够不与附加膜等等一起使用本发明。
本发明具有远超过尤其也用于该目的的常规离子交换器的能力的非常高的有毒重金属能力。
本发明忽略非重要组成部分的浓度,例如不受影响的钠、钙、镁等等。
Claims (17)
1.水净化滤筒,所述滤筒具有带有至少一个进水口(102)的筒上部(101)、带有至少一个出水口(113)的筒下部(110)以及围壁(11),其中所述筒下部(110)和/或所述筒上部(101)是可移动的,其中所述滤筒内部中具有一床,所述床包括平均粒径大于50μm到1000μm的含羟基或氨基基团的交联聚合物多孔粒子,并且其中所述床体积与所述床正面面积的比在大约0.03到大约1.5的范围内。
2.根据权利要求1所述的滤筒,其中所述床体积与所述床正面面积的比在大约0.1到大约1.0的范围内。
3.根据权利要求1所述的滤筒,其中所述床体积与所述床正面面积的比在大约0.03到大约0.05的范围内。
4.根据权利要求1或2所述的滤筒(100),其中多孔渗透膜沿流动方向上布置在床上侧和/或床下侧上。
5.根据上述权利要求任一项所述的滤筒,其中所述多孔渗透膜具有直径从5到10μm的小孔。
6.根据上述权利要求任一项所述的滤筒,其中将所述床布置为垂直或径向可灌注。
7.根据上述权利要求任一项所述的滤筒,其中所述多孔粒子具有从100%干燥粒子开始的在水中300%的最大膨胀系数。
8.根据上述权利要求任一项所述的滤筒,其中所述多孔粒子具有100-500μm的平均粒度。
9.根据上述权利要求任一项所述的滤筒,所述滤筒另外包括移除微量污染物的材料,优选地为活性碳。
10.根据上述权利要求任一项所述的滤筒,其中所述多孔粒子和所述移除微量污染物的材料布置在所述滤筒内的不同区域中。
11.根据上述权利要求任一项所述的滤筒,其中所述多孔粒子和所述移除微量污染物的材料存在于所述滤筒内的混合物中。
12.根据上述权利要求任一项所述的滤筒,其中所述多孔粒子的干容重在0.25g/ml到0.8g/ml的范围内。
13.根据上述权利要求任一项所述的滤筒,其中所述含羟基或氨基基团的交联聚合物在其侧链基团中被衍生化。
14.根据上述权利要求任一项所述的滤筒,其中基于聚合物中可交联基团的总数,所述含羟基或氨基基团的交联聚合物具有至少10%的交联度。
15.根据上述权利要求任一项所述的滤筒,其中采用反向尺寸排阻色谱法测定,所述多孔粒子的平均孔径大小在1nm到100nm的范围内。
16.根据权利要求1到15任一项所述的滤筒用于移除水中金属和重金属的用途。
17.用于移除水中金属和重金属的方法,其中所述水通过根据权利要求1到15任一项所述的滤筒。
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EP16176161.4A EP3173146A1 (de) | 2015-11-27 | 2016-06-24 | Poröses polymermaterial zur bindung von metall-haltigen ionen oder zur reinigung von organischen molekülen |
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DE102019106646A1 (de) * | 2019-03-15 | 2020-09-17 | Instraction Gmbh | Partikel mit biozider Beschichtung |
DE102021120424A1 (de) | 2021-08-05 | 2023-03-23 | Instraction Gmbh | Entfernung von Viren aus Wasser durch Filtration |
CN116813417B (zh) * | 2023-08-25 | 2023-11-03 | 云南省生态环境科学研究院 | 一种针对重金属污染土壤的智能控释肥料及其制备方法 |
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