CN1127519A - 蒸汽裂化器中回收塑料的方法 - Google Patents
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- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
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Abstract
蒸汽裂化器中废塑料的回收方法,其中,在400至550℃下,将由废塑料得到的熔融物转化成多种产物,在180-280℃下,从这些产物中分离出一种馏出物馏分,并将其作为原料输回蒸汽裂化器中。
Description
本发明涉及一种蒸汽裂化器中回收塑料的方法。
以本发明方法可将塑料,例如纯聚合物废塑料、包括可能有的异物、粘结标签材料、填料、其它所含物等等在内的混合废塑料或废薄片,转化成供已知蒸汽裂化法用的高价值原料。这些原料在已知的蒸汽裂化法中又转化成裂解产物,例如乙烯、丙烯、C4-混合烃、裂解汽油等等,而且这些裂解产物以比蒸汽裂化法用惯用原料如粗挥发油、液化石油气(LPG)和汽油作原料时几乎相同甚或更高的产率形成。因此,用本发明方法就可以在蒸汽裂化法中以由废塑料制得的原料来代替上述的惯用原料,而且将粗挥发油、液化石油气和汽油与由废塑料得到的原料混合,就不是必要的了。
因此,本发明方法在塑料回收方面对国民经济作出了重要贡献。
通常,已知的蒸汽裂解法系指,在最高达650℃的温度下,将原料蒸发和加热,接着在蒸汽存在下,在一般为700-1100℃,例如为780-860℃的温度下,在通常为0.02-10秒,例如为0.1-2秒的时间内进行处理。
众所周知,垃圾中出现的废塑料,约70%(重量)为聚烯烃如聚乙烯和聚丙烯,约15%(重量)为苯乙烯聚合产物,约10%(重量)为PVC,以及约5%(重量)微不足道量的量其它塑料如聚氨酯、聚酯及聚酰胺。这些废塑料一般都沾有异物,也就是说,它们还含有粘结标签材料(Aufklebermaterialien)、填料、其它含容物等等。通常,废塑料都经过分拣,因此产生各自均为人们所知的不同碎片。可提及的是主要由聚烯烃如聚乙烯或聚丙烯构成的瓶子、容器等产生的碎瓶、碎吹胀成型体;主要由聚乙烯(PE)、聚丙烯(PP)、苯乙烯聚合产物如聚苯乙烯(PS)和聚氯乙烯(PVC)组成的混合塑料碎片;主要由PE和PP等构成的薄片碎片,以及主要由PE、PP和PS组成的轻质碎片;上述各种碎片都可能有粘附的异物、粘结标签材料、填料、其它含容物等等。在这种情况下,主要意指,这些碎片仅仅含有微不足道量不同于所提及的塑料的杂质,例如小于10%(重量),在很多情况下小于5%(重量),并且尤其小于2%(重量)。
为了将废塑料转化成可进一步加工的产物,已有一系列方法为人们所知,并已记载于专利文献中,其例子如催化法或热裂法、加氢裂化法、挤压法等等。举例来说,欧洲专利申请0 502 618中记载了一种方法,其中将废塑料,特别聚烯烃转化成低级烃。在该方法的情况下,将上述废塑料置于流化床装置中,在大约300-630℃的温度下进行转化。以此方法产生的低级烃如石蜡和蜡可以用已知的蒸汽裂解法转化成烯烃。经将流化床装置与已知的蒸汽裂解法相结合,就可以将废塑料转化成上述链烯烃。
这种方法的缺点显然是,必须向所得的蒸汽裂解法原料中添加粗挥发油,就是说,废塑料要转化成裂解产物如乙烯、丙烯等,不添加习用原料是行不通的。此外,还证明流化床中的固态物处理总是有缺点的。除此之外,这样一种方法的扩大规模在使用大型机器设备的技术等级上是成问题的。
在于1993年9月16日公开的专利申请WO093/18112中,记载了一种用废塑料制造链烯烃的方法,其中通过在380-680℃的温度范围内对废塑料进行热预处理来建立所期望的粘度,并接着在700-1100℃下对产物进行热处理。该方法不涉及产物的蒸馏分离。用该方法不能产生无残留物的可蒸发产物。
本发明的目的是提供一种方法,该方法可大规模工业使用,以废塑料转化成供可能已有的蒸汽裂解器使用的高价值原料,从而由这些原料不需添加粗挥发油、液化石油气和汽油就可在蒸汽裂解法中,以高产率制得裂解产物,例如乙烯、丙烯、C4-混合物和裂解汽油。
本发明的上述目的是这样来实现的:在400至550℃下,将由废塑料得到的熔融物转化成多种产物,在180-280℃下,优选220-260℃,特别是230-250℃,从这些产物中分离出一种蒸馏物馏份,并将其作为原料输回蒸汽裂化器中。
该方法的一个优选实施方案以下列工艺特征来表征:
-熔融废塑料,通常在280-380℃进行,
-将熔融物输入一个反应器,在该反应器中,于400至550℃下,将聚合物转化成多种产物,它们可在蒸汽裂解器中被蒸发并以常规方式裂化,
-在200至280℃,优选220-260℃,更优选230-250℃下,从这些所得产物中蒸馏分离出一种馏出物馏份,
-除残留物与固态物、无机酸及可能有的芳烃之外,将其余的产物输回反应器中,
-必要时经再次分离后,将分离出来的馏出物馏份作为原料导入蒸汽裂化器中。
在有些情况下,于馏出物馏份用于蒸汽裂解器之前,先将芳烃如乙基苯和苯乙烯从其中分离出来,证明是有利的。这可以用已知的各种方法如萃取或蒸馏来实现。然后可将芳烃供给分别的用途,例如直接添加到蒸汽裂解器产物的芳烃馏份(裂解汽油)中。
有利的是,将该方法用于吹胀成型体碎片和薄片碎片。此时,废塑料的熔融优选在280-350℃,有些情况下在300-350℃,尤其290-320℃时进行,而且反应器中的转化在400-450℃下进行。
优选以下列工艺步骤分离出馏出物馏份或诸馏出物馏份:
-借助一座直接置于管式炉之后的第一塔,将所得各产物分离成:
-一种在300至420℃时,尤其330-380℃时产生的塔底产物,该产物在除去残留物和固态物后被输回反应器,和
-一种在200至280℃时,优选220-260℃时特别是230-250℃产生的塔顶产物,该产物在部分冷凝后,在70至150℃,尤其100-120℃时被输向第二塔,
-用上述第二塔将部分冷凝后产生的液体/气体混合物分离成
-一种一般于50-100℃从第二塔塔底抽出的液体混合物,该混合物一方面返回第一塔,另一方面被用作蒸汽裂化器的原料,
-一种一般于20-80℃从第二塔塔顶抽出的气体混合物,该混合物被用作蒸汽裂化器的原料。
如果废塑料中有一些有意义的组份,也即一般大于5%(重量)的含氯塑料如聚氯乙烯及/或含芳烃塑料如苯乙烯聚合产物,例如在一种混合塑料碎片中,则已证明有利的是,将废塑料在330-380℃,尤其在320-350℃熔融,其间聚氯乙烯同时脱卤化氢,并在反应器中于410-530℃,优选420-480℃,尤其430-480℃下转化成产物。所得产物可在蒸汽裂解器中以传统方式蒸发并裂解。
通常为了脱去卤化氢,所用的停留时间为1-20小时就足够了。所需时间视所需的脱卤化氢程度而定,并可由本领域技术人员采用简单的初步试验就可确定。在某些情况下,特别是在熔融后连续地进行脱卤化氢时;例如在250-300℃,所需停留时间可至多约达5天。这可在暂时贮存过程中有利地进行。
优选以下列工艺步骤分离出馏出物馏份:
-借助一座直接置于反应器之后的第一塔,将所得各产物分离成:
-一种在330至450℃时,尤其350-400℃时产生的塔底产物,该产物在除去残留物和固态物后被返回反应器,和
-一种在200至280℃时,优选230-250℃时产生的塔顶产物,该产物在部分冷凝后,在70至150℃,尤其100-120℃时被输向第二塔,
-用上述第二塔将部分冷凝后产生的液体/气体混合物分离成:
-一种一般于50-100℃从第二塔塔底抽出的液体混合物,该混合物一方面被返回第一塔,另一方面供给适于除去芳烃的蒸馏装置或提取装置,
-一种一般于20-80℃从第二塔塔顶抽出的气体混合物,该混合物被用作蒸汽裂化器的原料。
供给上述蒸馏装置或萃取装置的液体混合物,一般分离成:
-一种液态馏份,该馏份被用作蒸汽裂解器的原料,和
-一种芳烃馏份。
第一塔塔顶产物的冷凝热可以用来产生不同压力的水蒸气。
废塑料的熔融,可在能够保证充分传热和所需彻底混合的相宜装置中进行。如果搅拌容器如搅拌锅或特别强力搅拌锅能经得起使用,则可配以加热套及/或内加热器。通常,熔融过程相当快,也就是说,在0.5-30min后即行结束。有利的是,例如在脱卤化氢时,使多个,例如两个或三个这种搅拌容器级联运作。
将熔融物转化成产物的反应器,可以使用习常所用的装置,例如搅拌容器或挤压机。以使用管式炉为有利。在许多情况下,已证明有利的是,将一部分离开管式炉的反应产物重又输入管式炉,以延长滞留时间。在进行这种操作时,转化成产物的反应根据温度状况和滞留时间状况,有一部分在为此所用的回输管道中发生,如需要,在一个滞留容器中发生。管式炉一般牵涉到一种热交换器,其中从处于管外的气体相中释出的热,被传给管中的物质,例如熔融物。有利的是,可以使用重整炉、炼焦炉、精炼炉,或者尤其一种管式裂化器,正如蒸汽裂解器中所用的管式裂化器(参见例如Ulmanns Encyklopadie der technischen Chemie,第4版,第3卷,第476页及第330/331页)。
生成产物的转化以在排除空气的条件下,例如在氮气氛下发生为有利,这样可避免热解过程中发生氧化反应。
本发明所指的残留物和固态物质,是蒸馏分离时残留的,而且即使沸腾的化,也不在低于500℃的温度下沸腾的那些物质。举例来说,它们涉及存在于废塑料中的杂质、残留纸、焦化产物、玻璃残渣与残留金属、砂子、残留颜料、填料或类似物。
本发明方法已被证明有利的是,第一塔的塔底产物在重又输回反应器之前,至少有一部分作为加热介质输经熔融容器的加热套。反应器中的平均滞留时间,通常为0.05-10小时。
本发明方法一般在0.8-2.0bar的压力下进行,优选在大气压力,即1bar下进行。起始沸点或沸程是以1bar为基础的。
废塑料可未经干燥或经干燥后使用。视熔融装置及其给料装置的尺寸而定,可能需要将废塑料以众所周知的方法如切碎或碾碎加以破碎。以2-10mm的平均粒度,可得到良好的结果。1-10cm的粒度,在一些情况下即使未经破碎的废塑料,同样也适用。
本发明方法的其它特征是各从属权利要求的主题。
下面用一个简化的工艺流程图来详细阐明本发明;图1。
经由输送机1--例如一台螺旋运输机--将经干燥并破碎过的废塑料2,例如吹胀成型体碎片从储罐3输至设有加热套的搅拌容器4。在该搅拌容器中,将废塑料于约300℃下转变成易泵送的熔融物。与此同时,可进行脱卤化氢,以备万一由于废塑料分拣上的差错而漏过一些含PVC的废塑料。可能产生的HCl5用水按已知方法--非本发明关键--转化成含水的HCl,可将其输至另外的生产工艺中,或者用NaOH中和之。上述熔融物用泵--强制循环--输至管式裂化器6(以下简称裂化器)。在该裂化器中,聚合物不需添加氢、水蒸气、催化剂、溶剂或稀释剂即可转化成可以在蒸汽裂解器中以习常方法蒸发并裂解的产物。在这种情况下,约在420℃下进行热力液体裂解(einethermische Fluessigspaltung),此外在可能有的情况下,还在裂化器中进行再次脱除卤化氢。所需的热量由外部,例如经油热或气热供给。离开裂化器的液体-水蒸气混合物直接供给塔7,例如浓缩塔。约在350℃时,将沸点更高、不能转化成短链烃的产物作为塔底产物抽出。所抽出的塔底产物,一方面直接返回裂化器,另一方面作为载热体被导经搅拌容器中的熔融物和搅拌容器的加热套,并最后返回裂化器。在上述塔底产物从塔中出来后,从该产物中除去残留物和固态物8,例如借助于水力旋流器9。约在240℃下从塔顶出来的蒸汽混合物经部分冷凝后,在约110℃下被输至另一座塔10,例如填充塔。进入填充塔的液/气混合物用水或NaOH水溶液11逆流洗除;可能还含于气体中的HCl以含水HCl或NaCl水溶液的形式随液体混合物一起从塔底排出。从塔底出来的液体混合物(=有机液体/含水HCl或NaCl水溶液)在后置的相分离容器12中进行分离。较轻的有机相一方面作为蒸汽裂解器的原料A排出工艺流程,另一方面以回流形式输向塔中。较重的水相可能富集了HCl或者NaCl13,将其从工艺流程中排出。从填充塔塔顶出来、不含HCl的气体混合物同样作为蒸汽裂解器的原料B输向蒸汽裂解器。
另外,上述简化的工艺流程图举例来说,也适合混合塑料碎片,图2。
经由输送机1--例如一台螺旋运输机--将破碎过的干燥废塑料2,例如混合塑料碎片从储罐3输至设有加热套的搅拌容器4。在该搅拌容器中,将废塑料于约350℃下转变成易泵送的熔融物。与此同时,脱卤化氢,以PVC中的氯含量为准计,脱除率达98-99%。产生的HCl 5用水按已知方法--非本发明关键--转化成含水HCl,可将其输至另外的生产工艺中,或者用NaOH中和之。上述熔融物用泵--强制循环--输至裂化器6。在该裂化器中,聚合物不需添加氢、水蒸气、催化剂、溶剂或稀释剂即可转化成可在蒸汽裂解器中以习常方法蒸发并裂解的产物。在这种情况下,约在450℃下进行热力液体裂解(einethermische Fluessigspaltung),此外,还在裂化器中再次脱除残留的卤化氢。所需的热量由外部,例如经油热或气热供给。离开裂化器的液体/水蒸气混合物直接供给塔7,例如浓缩塔。约在380℃时,将沸点更高、不能转化成短链烃的产物作为塔底产物抽出。所抽出的塔底产物,一方面直接返回裂化器,另一方面作为载热体被导经搅拌容器中的熔融物和搅拌容器的加热套,并最后返回裂化器。在上述塔底产物从塔中出来后,从该产物中除去残留物和固态物8,例如借助于水力旋流器9。约在240℃下从塔顶出来的蒸汽混合物经部分冷凝后,在约110℃下被输至另一座塔10,例如填充塔。进入填充塔的液/气混合物用水或含水NaOH11逆流洗除;含于气体中的HCl以含水HCl或NaCl水溶液的形式随液体混合物从塔底一起排出。从塔底出来的液体混合物(=有机液体/含水HCl或NaCl水溶液)在后置的相分离容器12中进行分离。较轻的有机相--见表11--一方面输向适合用来除去芳烃的蒸馏装置或萃取装置20,另一方面返回塔中。较重的水相富集了HCl或NaCl13,将其从工艺流程中排出。从填充塔塔顶出来、不含HCl的气体混合物作为蒸汽裂解器的原料D输向蒸汽裂解器。上述输至蒸馏装置或萃取装置的有机液体,一方面分离成蒸汽裂解器原料C,另一方面在塔20中分离成芳烃馏份X;这两种馏份均排出工艺流程。
不言而喻,当上述方法特征在常规工艺技术范围内被专业人员稍加改变,根本的创造性仍维持不变。
所得原料可以在蒸汽裂解器中以常规方式蒸发或裂解。
此外,本发明方法还有一个优点是,在用从废塑料中得到的有价值产物运行蒸汽裂解器时,比以粗挥发油作原料能节省热能。该方法不需添加氢、稀释剂或溶剂也能进行,而且实际上可以不增压工作。该方法的另一优点是,对蒸汽裂解器供应了可不留残余物地蒸发的原料。
在有些情况下,已证明有利的是,按已知方法如Shell法或Texaco法(例如Ullmanns Encyklopadie der technischen Chemie,第4版,第14卷,第395-397页),例如在旋流气化器中,经常规气化可用排出的残留物与固态物8发生合成气。同时产生的残渣可予掩埋,或者用作建筑辅料。
由蒸发装置或提取装置20得到的芳烃--非本发明关键--常可进一步加工。这一般涉及一种以苯乙烯、乙苯、甲苯和苯为主成份组成的混合物。这些芳烃例如可在本身已知、象UllmannsEncyklopadie der technischen Chemie,第4版,第22卷,第293-309页中所述、将乙苯转化成苯乙烯的装置中用作原料。此外,它们还可以在双键加氢后,用于所谓的芳烃装置,在该装置中,用一种由苯、甲苯和混合二甲苯组成的混合物主要生产苯(Ullmanns Encyklopadie der technischen Chemie,第4版,第8卷,第383-411页)。
实施例1
在图1所示的上述装置中,对一种购自Duales SystemDeutschland GmbH(德国,波恩)的吹胀成型体碎片进行处理,该碎片的塑料成份主要是聚乙烯和聚丙烯,其中含有可能粘附的杂质、粘结标签材料、填料、其它含容物等等。以此产生的蒸汽裂解器原料A(液体混合物)和B(气体混合物),其组成如表所示,表1和2。
以此由蒸汽裂解法得到的裂解产物,其组成如表所示,表3和4。为比较起见,上述二表中还列出蒸汽裂解器以习用原料粗挥发油工作时的裂解产物组成。比较表明,蒸汽裂解器以得自吹胀成型体碎片的原料工作时,乙烯和丙烯的产率高于蒸汽裂解器以粗挥发油工作时的产率。转化吹胀成型体碎片时,废塑料转化如下:有机液体混合物=蒸汽裂解器原料A =74.0%(重量)无HCl的气体混合物=蒸汽裂解器原料B =16.0%(重量)残留物(有机高沸烃) = 2.5%(重量)固态物(灼烧残渣) = 7.5%(重量)
100.0%(重量)因此,有机成份=92.5%(重量)
实施例2
在图2所示的上述装置中,对一种购自Duales SystemDeutschland GmbH(德国,波恩)的混合塑料碎片进行处理,该碎片的塑料成份主要是聚乙烯、聚丙烯、苯乙烯聚合产物和聚氯乙烯,其中含有可能粘附的杂质、粘结标签材料、填料、其它含容物等等。以此产生的蒸汽裂解器原料C(液体混合物)和D(气体混合物),其组成如表所示,表12和13。
以此由蒸汽裂解法得到的裂解产物,其组成如表所示,表14和15。废塑料的混合塑料碎片转化结果如下:有机液体混合物=蒸汽裂解器原料C =34.2 %(重量)无HCl的气体混合物=蒸汽裂解器原料D =21.8 %(重量)芳烃馏份,主要为乙苯和苯乙烯 =25.8 %(重量)残留物(有机高沸烃) =12.0 %(重量)固态物(灼烧残渣) = 5.0 %(重量)HCl = 1.2 %(重量)
=100.0%(重量)因此,有机成份=93.8%(重量)下列各表适用下面诸缩略词:HC=烃, NA=非芳烃, EB=乙苯
表1:吹胀成型体碎片
原料A=供给蒸汽裂解器的液体混合物
得自本发明方法
组成 | 〔%(重量)〕 |
C3HC | 0.01 |
丁烯-1 | 0.05 |
其它丁烯 | 0.04 |
正丁烯 | 0.04 |
戊烯-1 | 0.20 |
其它戊烯 | 0.16 |
组成 | 〔%(重量)] |
异戊烯 | 0.01 |
正戊烯 | 0.32 |
其它C6HC | 0.48 |
甲基环戊烯 | 0.12 |
己烯-1 | 1.79 |
甲基环戊烷 | 0.07 |
其它己烯 | 0.24 |
正己烷 | 1.08 |
甲基环己烯 | 0.84 |
其它C7HC | 0.86 |
庚烯-1 | 2.50 |
甲基环己烷 | 0.33 |
正庚烷 | 2.34 |
辛烯-1 | 2.59 |
其它C8HC | 2.59 |
正辛烷 | 2.63 |
壬烯-1 | 3.59 |
其它C9HC | 3.42 |
正壬烷 | 3.02 |
其它C10HC | 1.40 |
癸烯-1 | 3.96 |
正癸烷 | 3.34 |
十一烯-1 | 3.48 |
其它C11HC | 1.45 |
正十一烷 | 2.88 |
十二烯-1 | 3.45 |
组成 | 〔%(重量)〕 |
其它C12HC | 1.75 |
正十二烷 | 3.41 |
十三烯-1 | 3.56 |
其它:C13HC | 2.04 |
正十三烷 | 3.73 |
其它C14HC | 2.16 |
十四烯-1 | 3.61 |
正十四烷 | 3.64 |
其它C15HC | 1.45 |
十五烯-1 | 3.33 |
正十五烷 | 3.58 |
其它C16HC | 1.23 |
十六烯-1 | 2.76 |
正十六烷 | 3.58 |
其它C17HC | 0.73 |
十七烯-1 | 2.18 |
正十七烷 | 3.43 |
其它C18HC | 0.17 |
十八烯-1 | 1.24 |
正十八烷 | 3.07 |
总计 | 100.00 |
表2:吹胀成型体碎片
原料B=供给蒸汽裂解器的气体混合物得自本发明方法
组成 | 〔%(重量)] |
H2 | 0.22 |
CH4 | 3.65 |
C2H6 | 8.89 |
C2H4 | 2.76 |
C3H8 | 13.16 |
C3H6 | 13.78 |
i-C4H10 | 0.22 |
n-C4H10 | 9.31 |
1-C4H8 | 7.83 |
i-C4H8 | 3.14 |
2-C4H8t | 1.80 |
2-C4H8c | 1.31 |
C4H6 | 0.93 |
i-C5H12 | 0.47 |
n-C5H12 | 11.51 |
C5H10 | 10.60 |
苯 | 0.71 |
C6H12 | 9.71 |
总计 | 100.00 |
表3:吹胀成型体碎片
蒸汽裂解器裂解产物I)按本发明方法用原料AII)用粗挥发油作原料
组成 | 单位[%(重量)]I II | |
CO | 0.1 | 0.2 |
H2 | 0.7 | 1.0 |
CH4 | 10.7 | 14.6 |
C2H6 | 3.6 | 3.1 |
C2H4 | 33.1 | 29.9 |
C2H2 | 0.4 | 0.5 |
C3H8 | 0.4 | 0.4 |
C3H6 | 16.8 | 15.2 |
丙炔 | 0.2 | 0.3 |
丙二烯 | 0.3 | 0.4 |
i-C4H10 | 0.0 | 0.0 |
n-C4H10 | 0.1 | 0.2 |
1-丁烯 | 2.1 | 1.4 |
异丁烯 | 0.7 | 2.1 |
2-丁烯(c) | 0.5 | 0.5 |
2-丁烯(t) | 0.4 | 0.3 |
C4H6 | 7.2 | 4.9 |
C5HC | 5.2 | 4.5 |
C6-C8NA | 1.8 | 2.1 |
苯 | 7.8 | 7.9 |
甲苯 | 2.9 | 3.5 |
组成 | 单位[%(重量)]I II | |
EB+二甲苯 | 0.6 | 1.1 |
苯乙烯 | 0.8 | 1.0 |
C9HC | 0.7 | 0.9 |
C10+HC | 3.0 | 4.0 |
总计 | 100.0 | 100.0 |
表4:吹胀成型体碎片
裂解产物-气体混合物-源自蒸汽裂解器I)按本发明方法用原料BII)用粗挥发油作原料
组成 | 单位[%(重量)]I II | |
CO | 0.2 | 0.2 |
H2 | 1.0 | 1.0 |
CH4 | 16.8 | 14.6 |
C2H6 | 6.5 | 3.1 |
C2H4 | 31.8 | 29.9 |
C2H2 | 0.7 | 0.5 |
C3H8 | 3.2 | 0.4 |
C3H6 | 16.1 | 15.2 |
丙炔 | 0.3 | 0.3 |
丙二烯 | 0.5 | 0.4 |
i-C4H10 | 0.0 | 0.0 |
n-C4H10 | 1.0 | 0.2 |
1-丁烯 | 1.0 | 1.4 |
异丁烯 | 0.9 | 2.1 |
2-丁烯(C) | 0.4 | 0.5 |
组成 | 单位[%(重量)]I II | |
2-丁烯(t) | 0.3 | 0.3 |
C4H6 | 4.9 | 4.9 |
C5HC | 2.6 | 4.5 |
C6-C5NA | 0.5 | 2.1 |
苯 | 6.0 | 7.9 |
甲苯 | 1.7 | 3.5 |
EB+二甲苯 | 0.3 | 1.1 |
苯乙烯 | 0.6 | 1.0 |
C9HC | 0.3 | 0.9 |
C10+HC | 2.3 | 4.0 |
总计 | 100.0 | 100.0 |
表11:混合塑料碎片
原料供给蒸馏装置或萃取装置以除去芳烃,得自本发明方法
组成 | [%(重量)] |
C2HC | <0.01 |
C3HC | 0.14 |
正丁烷 | 0.05 |
丁烯-1 | 0.21 |
其它丁烯 | 0.05 |
异戊烷 | 0.02 |
正戊烷 | 1.45 |
戊烯-1 | 0.24 |
其它戊烯 | 0.36 |
组成 | 〔%(重量)] |
正己烷 | 0.57 |
己烯-1 | 2.22 |
其它己烯 | 0.81 |
甲基环戊烷 | 0.12 |
甲基环戊烯 | 0.13 |
其它C6HC | 0.95 |
苯 | 2.93 |
正庚烷 | 1.03 |
庚烯-1 | 1.15 |
甲基环己烷 | 0.09 |
甲基环己烯 | 0.94 |
其它C7HC | 1.42 |
甲苯 | 6.72 |
正辛烷 | 1.02 |
辛烯-1 | 1.43 |
乙基环己烷 | 5.56 |
乙基苯 | 8.84 |
对二甲苯 | 0.27 |
间二甲苯 | 0.20 |
邻二甲苯 | 0.36 |
苯乙烯 | 9.64 |
其它C8HC | 1.37 |
正壬烷 | 1.83 |
壬烯-1 | 1.45 |
异丙基苯 | 1.58 |
正丙基苯 | 0.40 |
组成 | [%(重量)] |
其它C9HC | 4.43 |
正癸烷 | 1.92 |
癸烯-1 | 1.60 |
其它C10HC | 1.65 |
正十一烷 | 1.29 |
十一烯-1 | 1.36 |
其它C11HC | 3.43 |
正十二烷 | 1.41 |
十二烯-1 | 1.34 |
其它C12HC | 3.93 |
正十三烷 | 1.46 |
十三烯-1 | 1.53 |
其它C13HC | 4.05 |
正十四烷 | 1.43 |
十四烯-1 | 1.31 |
其它C14HC | 2.69 |
正十五烷 | 1.40 |
十五烯-1 | 0.78 |
其它C15HC | 1.61 |
正十六烷 | 1.44 |
十六烯-1 | 0.59 |
其它C16HC | 0.88 |
正十七烷 | 1.32 |
十七烯-1 | 0.28 |
其它C17HC | 0.15 |
正十八烷 | 1.05 |
十八烯-1 | 0.03 |
组成 | [%(重量)] |
其它C18HC | 0.09 |
正十九烷 | |
十九烯-1 | |
其它C19HC | |
总计 | 100.00 |
表12:混合塑料碎片
原料C供给蒸汽裂解器,得自本发明方法及
除去芳烃的蒸馏装置或萃取装置
组成 | [%(重量)] |
C2HC | 0.02 |
C3HC | 0.25 |
正丁烷 | 0.10 |
丁烯-1 | 0.37 |
其它丁烯 | 0.10 |
异戊烷 | 0.04 |
正戊烷 | 2.54 |
戊烯-1 | 0.42 |
其它戊烯 | 0.63 |
正己烷 | 1.00 |
己烯-1 | 3.89 |
其它己烯 | 1.40 |
甲基环戊烷 | 0.19 |
甲基环戊烯 | 0.21 |
其它C6HC | 1.53 |
组成 | [%(重量)] |
苯 | 5.11 |
正庚烷 | 1.42 |
庚烯-1 | 1.76 |
甲基环己烷 | 0.09 |
甲基环己烯 | 0.96 |
其它C7HC | 1.46 |
甲苯 | 1.99 |
正辛烷 | 0.02 |
辛烯-1 | 0.04 |
乙基外己烷 | 5.70 |
乙基苯 | 0.09 |
对二甲苯 | <0.01 |
间二甲苯 | <0.01 |
邻二甲苯 | 0.01 |
苯乙烯 | 0.18 |
其它C8HC | 0.01 |
正壬烷 | 0.11 |
壬烯-1 | 0.06 |
异丙基苯 | 0.09 |
正丙基苯 | 0.05 |
其它C9HC | 3.55 |
正癸烷 | 1.54 |
癸烯-1 | 0.98 |
其它C10HC | 1.01 |
正十一烷 | 2.20 |
十一烯-1 | 2.40 |
组成 | [%(重量)] |
其它C11HC | 5.90 |
正十二烷 | 2.50 |
十二烯-1 | 2.30 |
其它C12HC | 6.90 |
正十三烷 | 2.55 |
十三烯-1 | 2.67 |
其它C13HC | 7.08 |
正十四烷 | 2.53 |
十四烯-1 | 2.31 |
其它C14HC | 4.76 |
正十五烷 | 2.47 |
十五烯-1 | 1.38 |
其它C15HC | 2.85 |
正十六烷 | 2.52 |
十六烯-1 | 1.04 |
其它C16HC | 1.54 |
正十七烷 | 2.34 |
十七烯-1 | 0.50 |
其它C17HC | 0.26 |
正十八烷 | 1.82 |
十八烯-1 | 0.05 |
其它C18HC | 0.16 |
正十九烷 | 0.03 |
十九烯-1 | |
其它C19HC | |
总计 | 100.00 |
表13:
混合塑料碎片
原料D=供给蒸汽裂解器的气体混合物,得自本发明方法
组成 | [%(重量)] |
H2 | 1.32 |
CH4 | 8.29 |
C2H6 | 8.94 |
C2H4 | 10.40 |
C3H8 | 6.95 |
C3H6 | 20.49 |
i-C4H10 | 0.28 |
n-C4H10 | 2.25 |
1-C4H8 | 4.27 |
i-C4H8 | 6.77 |
2-C4H8t | 1.65 |
2-C4H8c | 2.32 |
C4H6 | 1.20 |
i-C5H12 | 0.18 |
n-C5H12 | 10.62 |
C5H10 | 7.51 |
苯 | 1.06 |
C6H12 | 5.50 |
总计 | 100.00 |
表14:
混合塑料碎片
裂解产物按本发明方法用原料C产自蒸汽裂解器
组成 | [%(重量)] |
CO | 0.1 |
H2 | 0.8 |
CH4 | 11.1 |
C2H6 | 3.0 |
C2H4 | 27.2 |
C2H2 | 0.4 |
C3H8 | 0.5 |
C3H6 | 13.8 |
丙炔 | 0.2 |
丙二烯 | 0.3 |
i-C4H10 | 0 |
n-C4H10 | 0.1 |
1-丁烯 | 1.5 |
异丁烯 | 1.3 |
2-丁烯(c) | 0.5 |
2-丁烯(t) | 0.3 |
C4H6 | 5.8 |
C5HC | 4.9 |
C6-C8NA | 1.7 |
苯 | 12.2 |
甲苯 | 5.0 |
EB+二甲苯 | 1.0 |
苯乙烯 | 1.5 |
组成 | [%(重量)] |
C9HC | 1.2 |
C10+HC | 5.5 |
总计 | 100.0 |
表15:
混合塑料碎片
裂解产物按本发明方法用原料D产自蒸汽裂解器
组成 | [%(重量)] |
CO | 0.2 |
H2 | 1.7 |
CH4 | 19.3 |
C2H6 | 6.7 |
C2H4 | 31.8 |
C2H2 | 0.7 |
C3H5 | 2.1 |
C3H6 | 16.1 |
丙炔 | 0.4 |
丙二烯 | 0.6 |
i-C4H10 | 0.1 |
n-C4H10 | 0.3 |
1-丁烯 | 0.9 |
异丁烯 | 2.0 |
2-丁烯(c) | 0.4 |
2-丁烯(t) | 0.3 |
1,3-C4H6+VA | 4.5 |
C5HC | 2.6 |
组成 | [%(重量)] |
C6-C8NA | 0.5 |
苯 | 5.1 |
甲苯 | 1.4 |
EB+二甲苯 | 0.2 |
苯乙烯 | 0.5 |
C9HC | 0.2 |
C10+HC | 1.5 |
总计 | 100.0 |
Claims (10)
1、蒸汽裂化器中回收废塑料的方法,其特征在于,在400至550℃下,将由废塑料得到的熔融物转化成多种产物,在180-280℃下,从这些产物中分离出一种蒸馏物馏份,并将其作为原料输至蒸汽裂化器中。
2、权利要求1所述的方法,其特征在于,包括下列方法特征:
-熔融废塑料,
-将熔融物输入一个反应器,在该反应器中,于400至550℃下,将聚合物转化成多种产物,
-在200至280℃下,从这些所得产物中蒸馏分离出一种馏出物馏份,
-除残留物与固态物及可能有的无机酸之外,将其余的产物输回反应器中,
-必要时经再次分离后,将分离出来的馏出物馏份作为原料导入蒸汽裂化器中。
3、权利要求1或2所述的方法,其特征在于,以下列工艺步骤从所得各产物中蒸馏分离出所述馏出物馏份:
-借助一座直接置于反应器之后的第一塔将所得各产物分离成
-一种在300至420℃时产生的塔底产物,该产物在除去残留物和固态物后被输回管式炉,和
-一种在200至280℃时产生的塔顶产物,该产物在部分冷凝后被输向70至150℃的第二塔,
-用上述第二塔将部分冷凝后产生的液体/气体混合物分离成:
-一种从第二塔塔底逸出的液体混合物,该混合物一方面返回第一塔,另一方面被用作蒸汽裂化器的原料,
-一种从第二塔塔顶逸出的气体混合物,该混合物被用作蒸汽裂化器的原料。
4、权利要求1或2所述蒸汽裂解器中回收含氯及/或含芳烃废塑料的方法,其特征在于,包括下列方法特征,
-在280-380℃下将废塑料熔融,使含氯废塑料脱卤化氢,
-将熔融物引入反应器,并在410-530℃下,将聚合物转化成多种产物,
-用直接置于反应器之后的第一塔将上述产物分离成,
-一种在330-450℃下产生的塔底产物,该产物在除去残留物和固态物后被输回反应器,和
-一种在200-280℃下产生的塔顶产物,该产物在部分冷凝后,于70-150℃下被输至第二塔,
-用上述第二塔将部分冷凝后产生的液体/气体混合物分离成:
-一种从第二塔塔底逸出的液体混合物,该混合物一方面返回第一塔,另一方面被输至一种适于除去芳烃的蒸馏单元或萃取单元,和
-一种从第二塔塔顶逸出的气体混合物,该混合物被用作蒸汽裂化器的原料。
5、权利要求4所述的方法,其特征在于,将输至蒸馏单元或萃取单元的液体混合物分离成:
-一种液体馏份,该馏份被用作蒸汽裂化器的原料,和
-一种芳烃馏份。
6、权利要求1至5中任何一项所述的方法,其特征在于,将一种由瓶子和容器构成的吹胀成型体的碎片用作废塑料,所述瓶子和容器主要由聚烯烃和可能有的杂质、粘结标签材料、填料、及/或其余含容物组成。
7、权利要求1至5中任何一项所述的方法,其特征在于,将一种主要由聚烯烃、聚苯乙烯和聚氯乙烯及可能有的杂质、粘结标签材料、填料、及/或其余含容物组成的混合塑料碎片用作废塑料。
8、权利要求1至5中任何一项所述的方法,其特征在于,将片材碎片用作废塑料,所述片材碎片主要由聚乙烯、聚丙烯、包括可能有的杂质、粘结标签材料、填料、其它含容物等组成。
9、权利要求1至5中任何一项所述的方法,其特征在于,将主要由聚乙烯、聚丙烯、聚苯乙烯等等组成包括可能有的杂质、粘结标签材料、填料、其它含容物等的轻质碎片用作废塑料。
10、权利要求1至5中任何一项所述的方法,其特征在于,还可在所述特定的塑料中添加少量垃圾中所含的废物,例如聚氨酯、聚酯、聚酰胺等。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4324112.3 | 1993-07-20 | ||
DE4324112A DE4324112C1 (de) | 1993-07-20 | 1993-07-20 | Verfahren zum Recyclen von Kunststoffen in einem Steamcracker |
DEP4400366.8 | 1994-01-10 | ||
DE4400366 | 1994-01-10 |
Publications (1)
Publication Number | Publication Date |
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CN1127519A true CN1127519A (zh) | 1996-07-24 |
Family
ID=25927795
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94192826A Pending CN1127519A (zh) | 1993-07-20 | 1994-05-20 | 蒸汽裂化器中回收塑料的方法 |
Country Status (14)
Country | Link |
---|---|
US (1) | US5731483A (zh) |
EP (1) | EP0710270B1 (zh) |
JP (1) | JP3312697B2 (zh) |
KR (1) | KR100294809B1 (zh) |
CN (1) | CN1127519A (zh) |
AU (1) | AU6970794A (zh) |
BR (1) | BR9407041A (zh) |
CA (1) | CA2167405A1 (zh) |
CZ (1) | CZ339495A3 (zh) |
DE (1) | DE59401485D1 (zh) |
ES (1) | ES2097051T3 (zh) |
FI (1) | FI960205A0 (zh) |
NO (1) | NO315615B1 (zh) |
WO (1) | WO1995003375A1 (zh) |
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US5481052A (en) * | 1992-04-22 | 1996-01-02 | Bp Chemicals Limited | Polymer cracking |
-
1994
- 1994-05-20 CN CN94192826A patent/CN1127519A/zh active Pending
- 1994-05-20 JP JP50487495A patent/JP3312697B2/ja not_active Expired - Fee Related
- 1994-05-20 WO PCT/EP1994/001647 patent/WO1995003375A1/de active IP Right Grant
- 1994-05-20 CZ CZ953394A patent/CZ339495A3/cs unknown
- 1994-05-20 DE DE59401485T patent/DE59401485D1/de not_active Expired - Fee Related
- 1994-05-20 BR BR9407041A patent/BR9407041A/pt not_active IP Right Cessation
- 1994-05-20 CA CA 2167405 patent/CA2167405A1/en not_active Abandoned
- 1994-05-20 US US08/553,658 patent/US5731483A/en not_active Expired - Fee Related
- 1994-05-20 KR KR1019960700242A patent/KR100294809B1/ko not_active IP Right Cessation
- 1994-05-20 ES ES94918352T patent/ES2097051T3/es not_active Expired - Lifetime
- 1994-05-20 EP EP19940918352 patent/EP0710270B1/de not_active Expired - Lifetime
- 1994-05-20 AU AU69707/94A patent/AU6970794A/en not_active Abandoned
-
1996
- 1996-01-16 FI FI960205A patent/FI960205A0/fi not_active IP Right Cessation
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002057391A1 (en) * | 2001-01-22 | 2002-07-25 | Chen, Yanping | Method and system of converting waste plastics into hydrocarbon oil |
CN103502393A (zh) * | 2011-05-05 | 2014-01-08 | Omv炼油和销售有限公司 | 用于高效节能地制备次生沉积物的方法和装置 |
CN103502393B (zh) * | 2011-05-05 | 2016-01-20 | Omv炼油和销售有限公司 | 用于高效节能地制备次生沉积物的方法和装置 |
US9920255B2 (en) | 2011-05-05 | 2018-03-20 | Omv Refining & Marketing Gmbh | Method and apparatus for energy-efficient processing of secondary deposits |
CN112888541A (zh) * | 2018-08-01 | 2021-06-01 | 瑞派科创新有限公司 | 分离多层塑料层的系统和方法 |
CN112888541B (zh) * | 2018-08-01 | 2023-03-28 | 瑞派科创新有限公司 | 分离多层塑料层的方法 |
CN114585710A (zh) * | 2019-10-24 | 2022-06-03 | 埃克森美孚化学专利公司 | 用于由塑料废物生产的液体的直接蒸汽裂化方法 |
CN114728881A (zh) * | 2019-11-07 | 2022-07-08 | 伊士曼化工公司 | 回收成分二醇酯 |
Also Published As
Publication number | Publication date |
---|---|
EP0710270A1 (de) | 1996-05-08 |
NO960236D0 (no) | 1996-01-19 |
DE59401485D1 (de) | 1997-02-13 |
NO315615B1 (no) | 2003-09-29 |
ES2097051T3 (es) | 1997-03-16 |
JPH09500412A (ja) | 1997-01-14 |
AU6970794A (en) | 1995-02-20 |
CA2167405A1 (en) | 1995-02-02 |
KR960704012A (ko) | 1996-08-31 |
US5731483A (en) | 1998-03-24 |
WO1995003375A1 (de) | 1995-02-02 |
KR100294809B1 (ko) | 2001-11-14 |
FI960205A (fi) | 1996-01-16 |
EP0710270B1 (de) | 1997-01-02 |
NO960236L (no) | 1996-01-19 |
FI960205A0 (fi) | 1996-01-16 |
CZ339495A3 (en) | 1996-05-15 |
JP3312697B2 (ja) | 2002-08-12 |
BR9407041A (pt) | 1996-03-12 |
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