CN116917102A - 处理复合薄片的方法 - Google Patents
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- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/04—Disintegrating plastics, e.g. by milling
- B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0203—Separating plastics from plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0293—Dissolving the materials in gases or liquids
- B29B2017/0296—Dissolving the materials in aqueous alkaline solutions, e.g. NaOH or KOH
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
公开了一种处理复合薄片的方法,所述复合薄片包括至少一个第一聚合物单层薄片,优选PET;第二聚合物单层薄片,优选PE;和至少一个粘合剂层,优选EVA或丙烯酸。所述薄片为小薄片形状,并通过将它们在热水中用至少一种二羧酸和至少一种脂肪酸,优选草酸和油酸进行第一振荡浴和用苛性试剂,优选苛性钠和表面活性剂进行第二振荡浴而分离;使用至少一个致密化浴来分离PE薄片和PET薄片。接着,使用振荡浴、干燥筒仓和用于分离异物颗粒的机器来处理所述PET薄片。每次浴处理后,除了在两个致密化浴之间之外,使所述小薄片通过离心机。
Description
技术领域
本发明属于废物处理以再利用领域,并提出了一种组分的处理复合薄膜从而以无害方式分离其组分的方法。
背景技术
由聚合物制成的薄片被用作制造各种包装的原料,特别是用于食品和制药行业。包装中最常用的聚合物是聚对苯二甲酸乙二醇酯(polyethylene terephthalate,PET)。
新鲜产品的包装通常由PET加上另一聚合物(通常是聚烯烃,例如聚乙烯(polyethylene,PE))的复合薄片制成。原因是,仅由PET薄膜制成的包装不适合用透明薄膜密封(需要较长的密封时间和较高的密封温度),这些包装通常就是这样呈现给公众的。
PET薄片和PE薄片由粘合剂粘合在一起,最通常的是乙烯-醋酸乙烯酯(ethylenevinyl acetate,EVA)或丙烯酸粘合剂,但也使用聚氨酯。可在粘合剂的顶表面放置乙基乙烯醇共聚物(ethyl vinyl alcohol,EVOH)层,以改善PET的气体阻隔性能。在一些情况下,在EVOH层的顶部放置第二粘合剂层。由此形成的薄片被称为PET/PE或PET/EVOH/PE。
用聚合物薄膜制造包装会产生边角料,这些边角料应该回收。使用过的包装也可以回收。与塑料一样,回收涉及材料的熔化。复合的PET/PE或PET/EVOH/PE薄膜的回收存在问题,因为不同材料的熔化会产生一种混浊(cloudy)的产品,其不能再用于生产透明的回收包装,而只能用于彩色包装。然而,由于彩色容器的需求量较小,因此它们必须以较低的价格出售,并且不能无限期地回收,因为必须将PE膜粘在回收的复合薄膜上的单个薄片上,这将导致所得的复合薄膜的逐渐弱化。这些问题将导致使用过的PET/PE过剩,无法被回收。
由于上述问题,希望通过预先分离组成其的各单个薄片来回收PET/PE或PET/EVOH/PE包装,这样得到的回收聚合物随后可以用于制造其他具有与原始原料相同特性的回收复合薄片,例如,它们可以用于生产透明包装。然而,由于粘合剂的存在,形成复合薄膜的各单个薄片的分离存在技术问题。
现有技术已经描述了用于处理复合薄膜的各种技术,包括分离它们的各种组分。在EP2650324B1(LINPAC PACKAGING LIMITED),2013年10月16日,“Process recycling ofplastic products”(“塑料制品的回收工艺”)中,通过剪切和加热(优选在80°至100°之间)物理分离第一种材料。
ES2211345( S.A.),2004年7月1日,“Procedimiento para la separación de polietilentereftalato a partir de láminas multicapa”[从多层薄膜中分离聚对苯二甲酸乙二醇酯的工艺],描述了一种方法,该方法包括使薄膜与含有水和醇的介质接触。ES2398079(SULAYR GLOBAL SERVICE,S.L.),2013年3月13日,“Procedimiento para la obtención de RPET(polietilentereftalatorecuperado)a partir de láminas complejas adhesivas con poliuretanos(从聚氨酯粘合剂复合薄膜中获得RPET(回收的聚对苯二甲酸乙二醇酯)的工艺)使用碱性碱液作为分离剂。
本专利主题的发明提出了一种分解复合薄膜的方法,该方法通过在水中用试剂连续浸泡来分离其组成成分而进行,所述试剂是无害的,不会在所得产品中产生难闻的气味。
发明内容
本发明涉及如权利要求1所限定的处理复合薄膜的方法。从属权利要求限定了其他实施方式。
实施该方法的起始材料是复合薄膜,通常来自挤压和热成型工业的废弃物,以及消费后的包装。
复合薄膜应理解为是指由多个单个薄膜组成的薄膜,其至少包括一个第一聚合物的薄膜和一个第二聚合物的薄膜。该复合薄膜包括至少一个粘合剂层。优选地,该第一聚合物是聚对苯二甲酸乙二醇酯(PET),第二聚合物是聚乙烯(PE),粘合剂是丙烯酸类,更优选地是乙烯-醋酸乙烯酯(EVA)。
本发明的目的是回收构成复合薄片的各单个薄片,去除粘合剂残留物和其他成分(EVOH、其他颜色的塑料颗粒、金属残留物),以便它们可以作为回收材料重新加入到生产链中。
复合薄片必须被分解成小颗粒(称为小薄片)。将生产废弃物和消费后包装研磨成小薄片是回收操作中的常见步骤。
一旦分解的复合薄片准备好,该方法分为三个阶段进行,这在现有技术中是已知的:分解各薄片、物理分离和对获得的各单个薄片的后续处理。
第一阶段或分解阶段是最相关的,因为它是技术难度最大的阶段。通过实施这一阶段,它从具有由至少两个彼此粘附的聚合物层组成的复合薄膜转变为由一种或另一种聚合物组成的单个薄膜。本发明提出的处理复合薄膜的方法的主要特征在于,用于分解复合薄膜的试剂是至少一种酸性试剂和至少一种苛性试剂。在优选的实施例中,酸性试剂是至少一种二羧酸(HOOC-R-COOH)和至少一种脂肪酸(R-COOH)的复合物。在更优选实施例中,所述至少一种二羧酸是草酸(HOOC-COOH),并且所述至少一种脂肪酸是油酸(C18H34O2)。在优选实施例中,所述至少一种苛性试剂选自由苛性钠(NaOH)和苛性钾(KHO)组成的组。
复合薄片的分解阶段包括以下子步骤:
-在含有至少一种二羧酸(优选草酸)和至少一种脂肪酸(优选油酸)的溶液的热水容器中对复合薄膜进行初始振荡浴。
-使薄片通过降低液体含量的机械装置,这是指任何机械装置,通过该机械装置,可以将薄片浸入水中之后所浸渍的液体基本去除。优选地,这样的装置是离心机。
-将薄片在热水罐中用选自苛性钠和苛性钾的苛性试剂进行第二振荡浴。在更优选实施例中,表面活性剂添加到该第二振荡浴中。
通过上述操作,材料已经被分解。下一阶段是对得到的各单个薄片进行物理分离,这包括将它们进行至少一次致密化浴,在此之后可以分别提取一种聚合物和另一种聚合物的小薄片。
从此之后,将分别处理一种聚合物和另一种聚合物的小薄片,在所提出的实施例中,方法集中在具有更高商业价值和对它们的回收有高监管要求的PET小薄片的处理上。
附图说明
本说明书由本质上说明性的且非限制性的附图补充说明,该附图描述了以下内容:
图1—处理复合薄片的操作顺序。
具体实施方式
在优选实施例中,该方法中使用的复合薄膜由聚对苯二甲酸乙二醇酯(PET)薄膜和聚乙烯(PE)层——它们用乙烯-醋酸乙烯酯(EVA)或丙烯酸类粘合剂粘合——组成。在不影响方法和所获得的结果的情况下,可以在粘合剂和PE层之间施加一个乙基乙烯醇共聚物(EVOH)层,或者在粘合剂和PE层之间施加额外的粘合剂层。
待处理的复合薄膜为小薄片的形式,尺寸约为12至15毫米。在该实施例中,处理了大约600kg数量的这些小薄片。
在第一阶段,分解所述小薄片。为此,使用本领域已知的具有振荡装置的容器,该容器通常由一个锥形圆柱状金属罐组成,在该金属罐内,对应于圆锥形顶点的部分布置有螺旋桨。
对于上述小薄片数量,在80°至90°的温度下,向罐中注入约2.5m3的水。将草酸和油酸加入水中。草酸已经溶解在水中,优选为10%的溶液。草酸溶液可商购获得。在一实施例中,施用12.5至37.5升10%的溶液,使得水罐内草酸的浓度在500ppm至1500ppm之间。在更优选的实施例中,将25升10%的溶液,即浓度为1000ppm的草酸,加入水罐中。在一实施例中,添加2.5至7.5升油酸(水罐内浓度为1000至3000ppm)。在更优选的实施例中,油酸的剂量为5升,即在水罐内的浓度为2000ppm。
将600kg的小薄片浸入罐中,并在振荡浴中进行约30分钟。
当振荡浴结束后,将小薄片从罐内取出,并将其引入减少液体成分的装置中,优选现有技术中已有类型的水平离心机,其中材料在一端进料,然后在另一端出料。在这些机器中,小薄片永远不会完全干燥,但含水量约为1.5%。
然后,将小薄片带到另一振荡罐中的第二浴中,该振荡罐具有与上述振荡罐相同的特性,并且具有相同体积的约2.5m3的水,在这种情况下,温度在70°至95°之间。从由苛性钠和苛性钾组成的组中选择的苛性试剂溶解在水中,在两种情况下,其浓度都在1%和5%之间,最优选2%。
在一优选实施例中,通常用于清洗PET瓶的表面活性剂也被添加到上述分解试剂中。表面活性剂的剂量约为每升水中1ml(1000ppm)。第二振荡浴持续约30分钟。
振荡罐内的机械摩擦和所使用的分解试剂将导致,在含有大量PET和PE复合薄片的情况下,现在罐内混合了大量单个的PET和PE薄片。
下一步是在罐内对PET和PE的小薄片进行物理分离,在罐中对它们进行第二振荡浴。为此,将大量的小薄片合并提取出并将其返回离心机。
随后,对它们进行第一致密化浴,之后将去除漂浮在水面上的PE小薄片。然而,底部仍有PE小薄片,将其与PET小薄片混合,因此要进行第二致密化浴,这将确保罐底部上剩余的PE小薄片上升到表面,之后可以将其去除,并且可以收集PET小薄片。
从此时开始,一种材料和另一种材料的小薄片将分别处理。
对于PE小薄片,对它们进行累积,当认为达到足够的量时,将它们进行干燥并聚集。至此,结束对这种材料的小薄片的处理。
该方法的其余步骤涉及PET小薄片的处理,这根据以下子步骤进行:
-将致密化浴后润湿的PET小薄片送入离心机中。
-在洁净的冷水中对其进行振荡浴,使从中取出的材料不含任何化学残留物。经过此浴后,小薄片的pH值约为7-8。
-使小薄片再次通过离心机。
-将它们装载到具有混合和干燥装置的容器中,所述混合和干燥装置例如现有技术中已知的混合筒仓和干燥筒仓。经过这种处理后,小薄片的含水量将低于1%,优选低于0.7%。
-一旦从筒仓中取出,将它们置于现有技术中已知的颗粒分离装置中。根据所使用的分离器类型,可以分离出有色颗粒、金属或PET以外的塑料等异物颗粒。
Claims (13)
1.一种处理复合薄膜的方法,至少包括第一聚合物的单层薄膜、第二聚合物的单层薄膜和至少一个粘合剂层,所述方法包括以下步骤:分解复合薄膜、分离各单个薄膜和进一步处理所述至少两个单层薄膜中的至少一个,其特征在于,用于分解所述复合薄膜的试剂是至少一种酸性试剂和至少一种苛性试剂。
2.根据权利要求1所述的处理复合薄膜的方法,其特征在于,所述至少一种酸性试剂是至少一种二羧酸(HOOC-R-COOH)和至少一种脂肪酸的复合物。
3.根据权利要求2所述的处理复合薄膜的方法,其特征在于,所述至少一种二羧酸(HOOC-R-COOH)是草酸,所述至少一种脂肪酸(R-COOH)是油酸(C18H34O2)。
4.根据权利要求1所述的处理复合薄膜的方法,其特征在于,所述至少一种苛性试剂选自由苛性钠(NaOH)和苛性钾(KHO)组成的组。
5.根据权利要求1所述的处理复合薄膜的方法,其特征在于,分解阶段包括以下子步骤:将小薄片置于热水和至少一种酸性试剂的溶液的振荡浴中;将所述复合薄膜置于减少液体成分的装置中,并在热水和至少一种苛性试剂溶液中进行第二振荡浴。
6.根据权利要求5所述的处理复合薄膜的方法,其特征在于,所述至少一种酸性试剂的溶液包括至少一种二羧酸(HOOC-R-COOH)和至少一种脂肪酸(R-COOH)。
7.根据权利要求5所述的处理复合薄膜的方法,其特征在于,在所述第二振荡浴中还添加表面活性剂。
8.根据权利要求1所述的处理复合薄膜的方法,其特征在于,分离阶段包括以下子步骤:将所述复合薄膜置于减少液体成分的装置中;将它们进行至少一次致密化浴;和分别提取所得的各单个薄片。
9.根据权利要求1所述的处理复合薄膜的方法,其特征在于,所述复合薄膜的第一薄膜由聚对苯二甲酸乙二醇酯(PET)制成,第二薄膜由聚乙烯(PE)制成。
10.根据权利要求1所述的处理复合薄膜的方法,其特征在于,至少一个需要进一步处理的单层薄膜是聚对苯二甲酸乙二醇酯(PET)薄膜。
11.根据权利要求10所述的处理复合薄膜的方法,其特征在于,对聚对苯二甲酸乙二醇酯(PET)薄膜进行进一步处理的阶段包括以下子步骤:将所述薄膜置于水中的振荡浴中,并将其置于带有混合和干燥装置的容器中。
12.根据权利要求11所述的处理复合薄膜的方法,其特征在于,在将PET薄膜置于水中的振荡浴之前和之后,对其应用减少存在于所述薄膜中的液体成分的装置。
13.根据权利要求11所述的处理复合薄膜的方法,其特征在于,在将所述PET薄膜置于带有混合和干燥装置的容器中之后,使所述PET薄膜通过异物颗粒检测装置。
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