CN110446608B - 回收包装材料的方法与装置 - Google Patents
回收包装材料的方法与装置 Download PDFInfo
- Publication number
- CN110446608B CN110446608B CN201780082737.4A CN201780082737A CN110446608B CN 110446608 B CN110446608 B CN 110446608B CN 201780082737 A CN201780082737 A CN 201780082737A CN 110446608 B CN110446608 B CN 110446608B
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- fluid
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- acid
- separation
- metal
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Abstract
公开了一种回收包装材料的方法。该包装材料包括含金属层(30)和至少一层聚合物层(20,40)的多层材料(10)。该方法包括将包装材料置于含分离流体(330)的大缸(310)内,产生来自金属层(30)的金属碎片、来自聚合物层(20,40)的塑料碎片、和残留组分的混合物。该分离流体包括含水、短链羧酸、磷酸、和碱金属氢氧化物溶液的混合物的混合物。
Description
技术领域
本发明包括一种分离流体及其用途,回收包装材料的方法与装置,所述包装材料包括含金属层和至少一层塑料层的多层材料。
背景技术
例如根据申请人的专利申请No.WO 2012/101189,微乳液分离流体用于分离层压体或多层材料的用途是已知的,该专利申请教导了多层材料中的各层彼此分离。这一W0'189公开内容的实施例涉及在光伏组件中所使用的多层材料的分离。
已讨论过改进在食品包装中所使用的层压体回收的要求。例如,Mario Abreu在“The recycling of tetra pak aseptic cartons”上的文章(发现于www.environmental- expert.com)深入地讨论了这一问题且注意到回收纤维素棉纸是可能的,但从铝箔中分离聚乙烯是不可能的。
美国专利No.5,421,526(Tetra Laval)教导了从含金属、塑料和可能地纸张或纸板层的层压包装材料废物中回收单独的材料组分,例如金属,塑料和纸张(若可用的话)的方法。通过用选自甲酸,乙酸,丙酸,丁酸和其他类似挥发性有机酸中的有机酸或有机酸的混合物处理废物,彼此分离各层。在比乙酸的闪点(在80%浓度下为约60℃)高的高温(80℃)下进行这一专利的方法,该方法不仅要求大量能量,而且增加安全风险。所使用的混合物是高度侵蚀性的,因为乙酸的浓度高(80%)。这一混合物将进攻铝箔组件并导致形成氢气,以及损失在该工艺中回收的铝量。
欧洲和专利申请EP 0 543 302 Al(Kersting)教导了从塑料箔,例如PE箔中分离铝箔,使得能回收铝的方法。将层压体置于低级脂肪酸(例如,乙酸,丙酸,甲酸,丁酸)的20%溶液并经10-20分钟加热至100℃。优选在密闭容器内进行该方法,在等于和/或高于其沸点下操作该液体。另外,当冷却该溶液时,可能出现降压。在EP'302中描述的这一方法的工业可行性是成问题的,因为必须一起加热铝和塑料箔形式的整个废物材料与溶液,并冷却以供每一装填循环。这可能难以采用大容器足够快速地实施且要求巨大量的能量。
类似地,中国专利申请CN 104744724涉及铝塑层压体的分离流体和通过利用分离流体,进行从塑料层中分离铝层的方法。主要通过混合40-200份蚁酸(甲酸)和5-10份二氯甲烷且还含有1-4份非离子表面活性剂,制备分离流体。这一申请的分离流体是高度挥发的且还含有对环境有害的组分。
中国专利申请No CN103131042涉及分离铝塑多层材料的另一类型的分离剂。通过以4:1-1:4的体积比混合蚁酸(甲酸)和乙醇,制备这类分离剂。通过使用分离剂,分离铝塑复合材料膜的方法包括下述步骤:混合分离剂和水,获得分离流体,和在该分离流体中浸泡清洁过的铝塑复合膜;和取出,清洁,离心并干燥。当铝塑分离膜浸泡在由分离流体和水混合的溶液中时,可有效地分离铝塑复合膜中的铝和塑料。在这一中国专利申请CN'042描述的实施例中,使用50-80℃的温度。这些是分离剂可燃且进攻铝时的条件,从而出现安全风险和铝的损失。
美国专利申请No.2002/0033475 Al(Bejarano)公开了一种用于回收保质期长的包装Tetra无菌纸盒的合成处理组合物。在这一专利申请中公开的组合物包括乳酸,乙酸钠,纤维素酶,α-淀粉酶,麦芽糖酶,柠檬酸和活性炭。使用这一组合物分离含纸张、聚乙烯和铝的多层材料。
国际专利申请No.WO 03/104315 Al(Masuria)教导了具有含纸张、铝和/或聚合物膜的多个层的复合材料的回收方法。在这一方法中,取决于层间所使用的粘合剂的特性,用不同溶剂,例如氯仿,四氢呋喃,二甲苯,质子羧酸或水处理复合材料。然而,在这一方法中,使用有机溶剂,如卤化介质具有负面的环境影响。
发明内容
在本发明的公开内容中教导了分离流体用于将多层材料的金属层与聚合物层分离的用途。该方法包括将多层材料置于具有分离流体的大缸中以供分离多层材料中各层。分离流体包括水、短链羧酸、磷酸以及碱金属氢氧化物的混合物。要理解短链羧酸和磷酸部分与碱金属氢氧化物反应,产生碱金属磷酸盐和碱金属羧酸盐。
所使用的短链羧酸是与水混溶的C1-C4单羧酸,例如甲酸,乙酸,丙酸和丁酸。在本发明的一个方面中,使用甲酸或乙酸。
碱金属氢氧化物包括,但不限于,锂、钠和钾的氢氧化物。一般地,可使用其他氢氧化物,若其他氢氧化物并不形成不溶磷酸盐的话,因为这些不溶盐将干扰铝的钝化,正如本说明书的方法中所教导的。
该分离流体具有与例如根据该中国专利申请已知的那些相比,对环境不那么有害的组分。有机成分的挥发性较低,这将最小化化学品的排放和***风险,因为这一文献以下列出的分离流体不会显示出可检测的闪点。
该方法也可包括与多层材料中的组分一起筛选/过滤分离流体,从分离流体中回收多层材料中的各组分,和之后分选,从金属层中获得第一级分的金属,和从聚合物层中获得第二级分的塑料。在本发明的一些方面中,可获得第三级分的不同种类的聚合物。这使得能够从多层材料中回收材料。所得聚合物可以挤出,和金属以金属碎片形式回收。
本发明的公开内容还教导了从包装材料,例如通用的饮料容器中回收聚合物组分和金属组分的方法。
还公开了回收包装材料的装置。该装置包括具有分离流体的大缸,将多层材料运输到大缸内的运输装置,和从分离流体和包装材料的组合中移除已分离材料的筛选/过滤装置。
要理解,在本发明公开内容中所使用的术语“多层材料”拟涵盖包括若干层材料的物体。若干层材料的非限制性实例包括其中一起层压、键合或胶合各层,或者材料之一可沉积在另一材料上的物体。多层材料可包括纸板层(这是饮料容器已知的),但不需要包括纸板层。
以下在非限制性实施方案中描述的方法用于回收饮料或食品容器中的层压体。然而,要理解,该方法也可应用到在其他应用中所使用的其他层压体的回收上。
附图说明
图1示出了在无菌包装中所使用的层压体的一个示意性实例,该层压体使用本发明公开内容的方法回收。
图2示出了使用本发明公开内容的教导的方法的流程图。
图3示出了使用本发明公开内容的教导回收的装置的概图。
具体实施方式
现基于附图描述本发明。要理解,本文描述的本发明的实施方案和各方面仅仅是例举且绝对不限制权利要求的保护范围。通过权利要求及其等价方案定义本发明。要理解,本发明一个方面或实施方案的特征可与本发明不同方面和/或实施方案的特征相结合。
图1示出了在无菌包装中所使用的层压体10的一个非限制性实例。层压体10包括粘结到铝层30上的第一聚合物层20,而铝层30本身粘结到第二聚合物层40上。在不同层之间使用粘结剂。这种粘结剂包括,但不限于,乙烯/丙烯酸共聚物和/或聚氨酯粘合剂。
在本发明的一个方面中,在无菌包装,例如在饮料例如果汁和牛奶以及番茄酱和类似流体用直立袋中所使用的无菌包装中,使用层压体10。类似包装还用于其他食品,例如快餐食品,以及化妆品。在一些应用中,聚合物层之一在一面上,或者视需要在两面上例如用产品说明书印刷。
在本发明的一个非限制性实例中,聚合物层20由低密度聚乙烯(LDPE)制造,和聚合物层40由聚对苯二甲酸乙二酯(PET)制造。金属层30由铝制造。这不是对本发明的限制,和可使用其他聚烯烃或塑料,例如聚丙烯(PP),聚酰胺或聚酯。类似地,金属层30可以是铝合金或其他金属。
一些类型的包装包括仅仅单一的聚合物层20和金属层30。例如,来自该生产的抛弃物(reject)可仅仅具有单一的聚合物层20和金属层30。其他类型的包装材料包括由相同聚合物制造的两层聚合物层20和40。本发明公开内容的教导也可应用到这些类型的多层材料上,且并不限制到所提及的多层材料上。
图3示出了概图,它是回收本发明公开内容的多层层压体10用的回收装置的实例。要理解,图3所示的装置仅仅是例举,而不是本发明的限制。多层层压体10如上所构造。
回收装置包括切割或粉碎装置300,它切割并粉碎由多层层压体10制造的包装材料捆(bale)50。切割或粉碎装置300紧跟着具有搅拌器320的大缸310,以搅动并搅拌大缸310的内容物。大缸310含有分离流体330和流体分配器340以供分配分离流体330到大缸310内。
可在筛选装置350中,从分离流体330中筛选材料,然后筛选出的材料在洗涤机360中用水洗涤。可在湿环境中,例如在湿式分选机370中,通过使用漂浮-下沉-分离或离心技术,进行从筛选过的材料中分离各组分的第一分选步骤。这通常导致两种材料物流。在以上概述的层压体10的非限制性实例中,两种材料物流之一基本上是低密度聚乙烯,和材料物流中的另一种是含铝和PET的混合物的混合物流。这两种材料物流可视需要在进一步的洗涤步骤中洗涤。
可在干燥单元380中干燥所得两种材料物流,和随后在干燥的分选单元390中纯化。可例如通过风筛或者电磁基技术,进行干燥分选,例如从混合物流中提取铝和PET。要理解,取决于要求,也可在单一装置中或者在多于两个装置中进行分选(湿式或干式)。
在流体回收装置355中,回收分离流体330,通过过滤和补充消耗的化学品,主要清洁掉杂质。在水循环装置365中,还回收洗涤水,以清洁洗涤水。循环包括交叉流过滤技术,反向渗透和/或液-液提取,它们还允许从洗涤水中回收分离流体330中的至少一些化学品。
图2示出了循环在图3所示装置中所使用的层压体10的方法的概述。层压体10以包装材料捆50形式一起收集。层压体10一般地在捆50中一起挤压,以减少其体积。可洗涤层压体10,在废物垃圾收集和/或加工装置处去除任何食品残留物。一旦到达回收装置,则首先将捆50置于切割和粉碎装置300内以供在步骤200中减少尺寸。然后在大缸310内负载切割/粉碎层压体10的坯料。在步骤210中,搅拌器320在大缸310中混合层压体10与分离流体300,生产混合物。
在步骤230中,进一步搅动并搅拌层压体10和分离流体330的混合物预定的处理时间,例如4小时,从而导致多层层压体10分离成其组成层,即LDPE的第一聚合物层20,铝层30和PET的第二聚合物层40(在以上描述的非限制性实例中)。一般地,分离流体330的效果是去除在LDPE的第一聚合物层20和/或第二聚合物层40与金属层30之间的粘合剂粘结,由金属层30生产金属碎片,和由第一聚合物层20和第二聚合物层40生产聚合物碎片。这在给定温度下,例如20℃至90℃之间在典型地30分钟至300分钟的处理时间期间内实现。在该方法的一个方面中,给定温度为70℃。在通用的饮料箱用方法的另一方面中,给定温度为30℃至50℃。温度和加工时间的选择主要取决于待脱层的粘合粘结剂的类型。与来自乙烯/丙烯酸共聚物的粘结剂一起粘结的层在约40℃下脱层,和具有来自聚氨酯粘合剂的粘结剂的那些在约70℃下脱层。
可从大缸310中移除分离流体330和分离材料,即LDPE,铝和PET的混合物,并在步骤240中,在筛分机350中筛分,以移除固体材料,所述固体材料包括来自第一聚合物层20的LDPE,来自第二聚合物层40的PET,和来自金属层30的大多数金属碎片。然后通过装置355,回收分离流体330。在步骤245中,通过过滤,和在步骤246中通过补充消耗的化学品,进行回收。然后将回收的流体往回置于流体分配器340中。在装置355中的过滤步骤245从分离流体330中移除基本上所有固体杂质,其中包括事先没有筛分出去的金属碎片。
在步骤240中筛分出去的固体材料是聚合物和铝的混合物。这一所得材料在步骤250中在洗涤机360中洗涤,然后在湿式分选步骤260中在湿式分选机370内借助漂浮-下沉-分离或离心技术分选成主要含LDPE的轻质材料,和主要含铝和PET的致密材料。轻质材料和致密材料在步骤270(轻质材料)和271(致密材料)中独立地干燥。干燥的致密材料在步骤280中在干式分选机390中借助风选或电磁技术,进一步分选,获得富含铝的材料和富含PET的材料。要理解,取决于要求,也可在一个步骤中,或者在大于两个步骤中,进行分选(湿式或干式)。
也在洗涤水再利用之前,洗涤水还需要在步骤255中用水循环装置365处理。这些处理包括采用常规和交叉流过滤技术,反向渗透和/或液-液提取的若干过滤步骤,它还允许从洗涤水中回收至少一些化学品并转移到流体回收装置355中以供再利用。在一个方面中,水循环装置365包括与反向渗透结合的液-液提取单元。
富含LDPE的材料可在步骤290中挤出成颗粒。金属碎片可在步骤291中挤压成粒料以供回收。类似地,富含PET的材料可以在步骤292中压缩以供运输。可例如通过挤出或挤压机,在装置395中进行后处理步骤290,291和292。
在大缸310中所使用的且来自于流体分配器340的分离流体330包括水,短链羧酸、磷酸和碱金属氢氧化物的混合物。短链羧酸例如是与水混溶的Cl-C4单羧酸,例如甲酸,乙酸,丙酸和丁酸。碱金属氢氧化物是锂、钠或钾的氢氧化物。在本发明的一个方面中,水是去离子水。短链羧酸和水的混合物降低多层材料中铝和粘合剂层之间的粘合分子间力。按序添加磷酸和碱金属氢氧化物,以控制铝溶解的副反应,正如下文所讨论的。
分离流体330保持在20℃至90℃之间,和在2至4的pH值下。取决于输入的层压体10或包装材料中其他多层材料的性能,选择实际值。通常低的pH值有利于分离性能,但也有利于导致铝溶解的副反应。理想地,本发明公开内容的方法在处理时间内实现足够高产率的来自金属层30的金属或者来自第一聚合物层20和第二聚合物层40的聚合物,同时保持金属层30的溶解最小。由于安全原因,金属层30的最小溶解是重要的,因为铝的溶解还导致形成氢气,氢气是***危险物。因此通过添加碱金属氢氧化物溶液到分离流体330中,来调节pH值。
分离流体330含有磷酸,或者备选地磷酸的盐(磷酸盐),以便控制分离流体330内溶解的铝含量。在合适的条件下,通过调节pH值,铝以磷酸铝形式沉淀。磷酸铝是微细分散的固体,它可在步骤245中从液体中过滤出来。
磷酸诱导在铝表面上形成磷酸铝的钝化覆盖薄层。这些表面磷酸盐充当抑制剂,从而部分钝化铝表面避免进一步的化学进攻。因此,添加磷酸将进一步最小化铝的溶解。
铝溶解和沉淀的总反应方程式是:
2Al(s)+2H3PO4(l)->2AlPO4(s)+3H2(g)
该反应产物留下固体形式或气体形式的分离流体330。磷酸被消耗且必须补充。这一补充以及其他化学品的补充在步骤246期间在回收装置355中发生。
在包装中使用的多层材料的其他实例
在包装材料中所使用的其他多层材料的非限制性实例包括用于咖啡包装和饮料包装中的LDPE(=低密度聚乙烯)/铝/PET,或者在咖啡包装和宠物食品包装中所使用的PP(=聚丙烯)/铝/聚酯层压体,或者在工业用粒状原材料的包装中或在牙膏管中使用的LDPE/铝/LDPE。另一实例是无菌的通用饮料箱的里面部分(聚合物和铝),它通常由LLDPE(=线性低密度聚乙烯)/铝/LLDPE组成。
应用实施例(实验室规模)
以下列出的组合物仅仅是合适配方的实例,且不是本发明的限制(所有百分比以重量计):
组合物1
水 | 45.7% |
冰醋酸 | 45.0% |
磷酸(30%溶液) | 3.0% |
氢氧化钠(33%溶液) | 6.3% |
组合物2
水 | 45.7% |
甲酸 | 45.0% |
磷酸(30%溶液) | 3.0% |
氢氧化钠(33%溶液) | 6.3% |
组合物3
水 | 45.7% |
丙酸 | 45.0% |
磷酸(30%溶液) | 3.0% |
氢氧化钠(33%溶液) | 6.3% |
组合物1-3阐述了具有不同短链羧酸的配方。
组合物4
水 | 45.7% |
冰醋酸 | 45.0% |
磷酸(30%溶液) | 3.0% |
氢氧化钾(33%溶液) | 6.3% |
组合物4阐述了采用氢氧化钾作为金属氢氧化物的配方。
以下列出的实施例仅仅是合适应用的实例且并不打算限制本发明。实施例1-5阐述了可用本发明范围内的分离组合物1处理的不同包装材料。实施例6-8阐述了分离流体的其他组合物的用途。
实施例1
在70℃下,用1kg分离流体(组合物1)搅拌60g LDPE/铝/PET材料(薄片,1cm2,来自饮料直立袋)。在2小时之后LDPE从铝中脱离完全,和在4小时之后,PET从铝中脱离完全。
实施例2
在70℃下,用1kg分离流体(组合物1)搅拌30g LDPE/铝/PET材料(薄片,3cm2,来自快餐食品包装)。在2小时之后LDPE从铝中脱离完全,和在4小时之后,PET从铝中脱离完全。
实施例3
在70℃下,用1kg分离流体(组合物1)搅拌60g LDPE/铝/LDPE材料(薄片,2cm2,来自牙膏管)。在2小时之后LDPE从铝中脱离完全。
实施例4
在70℃下,用20g分离流体(组合物1)搅拌PP/铝/PET薄片的三个单一样品(1cm2,层压体样品,如来自箔和变换器公司的咖啡包装)。在5小时之后,PP和PET从铝中脱离完全。
实施例5
在40℃下,用1kg分离液体搅拌30g LLDPE/铝/LLDPE+LLDPE材料(薄片,10cm2,无菌饮料箱的里面部分)。在2小时之后,铝从LLDPE中脱离完全。
实施例6
在70℃下,用20g分离液体(组合物2)搅振PE/铝/PET薄片的5个单一样品(1cm2,层压体样品,例如来自箔和变换器公司的咖啡包装)。在1小时之后,PE和PET从铝中脱离完全。
实施例7
在70℃下,用20g分离液体(组合物3)搅振PE/铝/PET薄片的5个单一样品(1cm2,层压体样品,例如来自箔和变换器公司的咖啡包装)。在10小时之后,PE和PET从铝中脱离完全。
实施例8
在70℃下,用20g分离液体(组合物4)搅振PE/铝/PET薄片的5个单一样品(1cm2,层压体样品,例如来自箔和变换器公司的咖啡包装)。在8小时之后,PE和PET从铝中脱离完全。
标记数字
10 多层材料
20 第一聚合物层
30 金属层
40 第二聚合物层
50 捆
300 切割或粉碎装置
310 大缸
320 搅拌器
330 分离流体
340 流体分配器
350 筛选装置
355 流体回收装置
360 洗涤机
365 水循环装置
370 湿式分选机
380 干燥单元
390 干式分选单元
395 后加工
Claims (21)
1.分离流体(330)用于分离多层材料(10)的用途,该多层材料(10)至少包括金属层(30)和聚合物层(20,40),该分离流体(330)包括水、短链羧酸、磷酸和碱金属氢氧化物的混合物,其中该分离流体(330)包括水和短链羧酸以分离多层材料(10),以及该分离流体(330)包括磷酸和碱金属氢氧化物以降低金属层(30)的溶解。
2.权利要求1的用途,其中短链羧酸,磷酸和碱金属氢氧化物在溶液中部分地反应,形成碱金属磷酸盐和碱金属羧酸盐。
3.权利要求1或2的用途,其中短链羧酸是与水混溶的C1-C4单羧酸。
4.权利要求3的用途,其中短链羧酸选自甲酸,乙酸,丙酸或丁酸。
5.权利要求1或2的用途,其中碱金属氢氧化物选自氢氧化锂,氢氧化钠或氢氧化钾。
6.权利要求1或2的用途,其中混合物中的组分包括30–60wt%短链羧酸,0.5–5wt%的30%磷酸溶液和2-8wt%的33%碱金属氢氧化物溶液,和30-60wt%水。
7.权利要求1或2的用途,其中混合物中的组分包括42-48wt%短链羧酸,2-4wt%的30%磷酸溶液和4-8wt%的33%碱金属氢氧化物溶液,和45-50wt%水。
8.权利要求1或2的用途,其中分离流体(330)的pH值为2-4。
9.将多层材料(10)中的金属层(30)与聚合物层(20,40)分离的方法,该方法包括:
将多层材料(10)置于含权利要求1-8任何一项的分离流体(330)的大缸(310)中。
10.权利要求9的方法,进一步包括下述中的至少一个:用分离流体(330)筛选或过滤(240)多层材料(10)中的组分,和之后分选(260,280),以从金属层(30)获得金属构成的第一级分,和从聚合物层(20,40)中获得塑料构成的第二级分。
11.权利要求9或10的方法,进一步包括回收分离流体(330)。
12.权利要求9或10的方法,其中在20℃至90℃的温度下进行分离。
13.权利要求9或10的方法,其中在70℃的温度下进行分离。
14.权利要求9或10的方法,其中分离流体的pH值为2至4。
15.权利要求9或10的方法,其中多层材料(10)包括至少一层铝层和由PET或PE组成的至少一层聚合物层(20,40)。
16.一种回收包装材料(300)的方法,所述包装材料(300)包括含至少一层金属层(30)和至少一层塑料层(20,40)的多层材料(10),其中该方法包括:
将多层材料(10)置于含权利要求1-8任何一项的分离流体(330)的大缸(310)内,以产生(260)如下物质的混合物:来自金属层(30)的金属碎片、来自聚合物层(20,40)的塑料碎片和残留组分。
17.权利要求16的方法,进一步包括分选(280)并分离金属碎片和塑料薄片,以生产金属颗粒。
18.权利要求16或17的方法,其中金属层(30)来自铝或其合金。
19.权利要求16或17的方法,其中至少一层塑料层(20,40)由聚烯烃制造。
20.权利要求16或17的方法,进一步包括回收分离流体(330)。
21.回收从多层材料(10)制成的包装材料的装置,该装置包括:
具有权利要求1-8任何一项的分离流体(330)的大缸(310);将多层材料(10)运输到大缸(310)内的运输装置;和用于从分离流体(330)和包装材料(10)的组合中移除(240)已分离材料的筛选/过滤装置(350)。
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CA3047048A1 (en) | 2018-06-21 |
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CN110446608A (zh) | 2019-11-12 |
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AU2017378087B2 (en) | 2022-09-01 |
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GB201621371D0 (en) | 2017-02-01 |
RU2019122114A3 (zh) | 2021-01-20 |
KR20190097153A (ko) | 2019-08-20 |
CO2019007371A2 (es) | 2019-08-20 |
JP2020515655A (ja) | 2020-05-28 |
MX2019007022A (es) | 2019-11-21 |
EP3554834B1 (en) | 2021-11-10 |
US20190351663A1 (en) | 2019-11-21 |
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MY193033A (en) | 2022-09-23 |
WO2018109147A2 (en) | 2018-06-21 |
RU2019122114A (ru) | 2021-01-15 |
BR112019012241A2 (pt) | 2019-11-05 |
DK3554834T3 (da) | 2022-02-14 |
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