CN116568779A - 用于处理液化废物聚合物的方法 - Google Patents
用于处理液化废物聚合物的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 229920000642 polymer Polymers 0.000 title abstract description 15
- 150000001993 dienes Chemical class 0.000 claims abstract description 35
- 238000004821 distillation Methods 0.000 claims abstract description 20
- 239000010779 crude oil Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000009835 boiling Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 239000004033 plastic Substances 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 239000003921 oil Substances 0.000 claims description 13
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- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 229910003294 NiMo Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 150000001336 alkenes Chemical class 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000006298 dechlorination reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- -1 bromine and fluorine Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- 239000003348 petrochemical agent Substances 0.000 description 1
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- 239000010817 post-consumer waste Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
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- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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Abstract
本发明涉及用于处理包含二烯烃的液化废物聚合物(LWP;10)的方法。将LWP进料供应至蒸汽汽提塔A以提供包含二烯烃和石脑油的馏出物(20)、以及底部馏出物(30)。使馏出物经受加氢处理B以产生二烯烃耗尽的馏出物(40),通过蒸馏C分离二烯烃耗尽的馏出物产生包含至少石脑油馏分(50)、任选的中间馏分(60)和底部馏分(70)的一种或多种馏分。石脑油馏分的氢化处理D产生适合作为用于蒸汽裂化器E的进料的氢化石脑油(80)。由于底部馏出物(30)、底部馏分(70)和中间馏出物(60)主要不含二烯烃,因此可以将它们与原油(90)混合并在炼油厂中进一步处理。
Description
技术领域
本发明涉及用于处理液化废物聚合物(LWP)的方法,具体地涉及使用蒸汽汽提塔的方法。
背景技术
使用油蒸馏单元的液化废物聚合物(LWP)(如废塑料热解油(WPPO)和水热液化的废塑料油)的处理不是直接的。LWP容易污染并且包含具有非常宽的沸点的不同组分。在原油(crude oil)蒸馏单元中,蒸馏将是可行的,但是来自原油蒸馏单元的产物通常导向不被设计用于烯烃进料的单元。例如,存在于LWP中的二烯烃可能在设计用于不包括这些组分的原油来源的石脑油馏分的氢化过程中引起问题。
LWP还含有不同的元素杂质,这主要取决于液化的聚合物废物的来源,而且还取决于所使用的液化技术。例如,在已认为是聚合物废物的潜在大规模来源的消费后废塑料(回收的消费塑料)中,最相关的杂质是氮、氧、硫和氯,但是也可以存在其它卤素,如溴和氟。含溴杂质主要可以包含在工业来源的聚合物废物(例如,来源于阻燃剂)中。此外,在LWP中也可以检测到金属及其它杂质,如来源于添加剂和污染物的类金属(metalloid)。这些杂质对LWP的直接利用具有不利影响。通过热解过程或水热液化所产生的LWP通常含有大量烯烃和芳香族化合物(aromatics,芳烃),它们中的每一种可能在一些下游过程(如升高的温度下的聚合(或焦化))中导致问题。
US5849964公开了通过所使用的材料解聚用于处理使用的或废塑料材料以回收化学原材料和液体燃料组分的方法,其被转化为可泵送相和转化为挥发相。一旦分离挥发相,则使剩余的可泵送相经受液相氢化、气化、低温碳化或者所述方法的组合。
WO2016142808公开了将废塑料转化为最终石化产品的集成方法。方法允许通过氢化处理(hydroprocessing,加氢处理,加氢操作)反应操作,所述氢化处理反应提供了满足蒸汽裂化器要求的规格的烃流组分的同时氢化和脱氯。
US20160264874公开了类似于WO16142808的方法,但是具有使所处理的烃流在精制区(polishing zone)中进一步脱氯的选择。
然而,仍需要处理废物聚合物的其它方法。
发明内容
下面呈现了简要总结以提供本发明的各个实施方式的一些方面的基本理解。本总结不是对本发明的广泛概述。它既不旨在鉴别本发明的重要或关键要素,也不旨在划定本发明的范围。以下总结仅以简化形式表示本发明的一些概念,作为本发明的示例性实施方式的更详细描述的前奏。
据观察当使用蒸汽汽提塔从LWP分离含有石脑油的馏分时,可以避免或至少减轻与LWP处理有关的一些问题。
根据本发明,提供了处理液化废物聚合物(LWP)的新方法,其中所述方法包括以下步骤:
a)提供包含二烯烃和石脑油的LWP流(stream,料流),
b)使LWP流经受蒸汽汽提塔以获得包含二烯烃和石脑油的馏出物、以及底部馏出物(distillate bottom,塔底馏出物),
c)使馏出物在氢气(hydrogen,氢)和一种或多种加氢处理(hydrotreatment)催化剂的存在下经受加氢处理反应条件以产生二烯烃耗尽的馏出物(diolefin depleteddistillate),以及
d)将二烯烃耗尽的馏出物分离成
·一种或多种馏分,包含:至少石脑油馏分,在大气压下沸点低于180℃;和任选的中间馏分,在大气压下沸点在180℃和360℃之间,和
·底部馏分(bottom fraction,塔底馏分)。
根据本发明,还提供了氢化石脑油作为蒸汽裂化器进料的新用途,其中氢化石脑油是通过包括以下的方法生产的:
a)提供包含二烯烃和石脑油的LWP流,
b)使LWP流经受蒸汽汽提塔以获得包含二烯烃和石脑油的馏出物、以及底部馏出物,
c)使馏出物在氢气和一种或多种加氢处理催化剂(hydrotreatment catalyst)的存在下经受加氢处理反应条件(hydrotreatment reaction condition)以产生二烯烃耗尽的馏出物,
d)将二烯烃耗尽的馏出物分离成
·一种或多种馏分,包含:至少石脑油馏分,在大气压下沸点低于180℃;和任选的中间馏分,在大气压下沸点在180℃和360℃之间,和
·底部馏分,以及
e)使步骤d)的石脑油馏分在氢气和一种或多种氢化处理催化剂(hydroprocessing catalyst,加氢处理催化剂,加氢操作催化剂)的存在下经受氢化处理反应条件(hydroprocessing reaction condition,加氢处理反应条件,加氢操作反应条件)。
根据本发明,还提供了原油和权利要求1的底部馏分的混合物作为炼油厂进料的新用途。
根据本发明,还提供了原油和权利要求1的中间馏分的混合物作为炼油厂进料的新用途。
在所附从属权利要求中描述了本发明的多个示例性且非限制性实施方式。
当结合附图阅读时,从具体示例性实施方式的以下描述中,将最好地理解本发明的各种示例性和非限制性实施方式和操作方法以及它们的其它目标和优势。
在本文档中作为开放性限制使用动词“包含”和“包括”,其既不排除也不要求未列举的特征的存在。除非另外明确说明,否则在从属权利要求中所列举的特征是可彼此自由组合的。此外,应理解在整个文档中,“一个”或“一种”(即单数形式)的使用不排除多个。
如本文所定义的,“氢化处理(hydroprocessing,加氢处理,加氢操作)”是指一系列的催化化学工程方法,包括加氢处理(hydrotreating)和加氢裂化(hydrocracking),其中将氢气的反应用于除去杂质(如氧、硫、氮、磷、硅和金属),饱和碳-碳键,断裂碳-碳键,降低平均分子量,重排进料的分子结构或它们的任意组合。
如本文所定义的,术语“加氢处理(hydrotreating)”是指化学工程方法,其中氢气的反应用于除去杂质(如氧、硫、氮、磷、硅和金属)和/或用于饱和碳-碳键,特别是作为炼油的一部分。
可以在一个或多个反应器单元或者催化剂床中在一个或多个步骤中实施加氢处理。
附图说明
以下参照附图更详细地解释本发明的示例性和非限制性实施方式以及它们的优势,其显示了用于处理包含二烯烃的液化废物聚合物10的示例性的非限制性流程图。
具体实施方式
本发明涉及用于处理液化废物聚合物(LWP)(如废塑料热解油)的方法。图1显示了方法的原理。因此,将包含二烯烃的LWP流10进料至蒸汽汽提塔容器A,其中分离出馏出物20和底部馏出物30。馏出物包含二烯烃和石脑油,而金属杂质主要保留在底部馏出物中。将馏出物进料至加氢处理单元B以产生二烯烃耗尽的馏出物40。当在氢气和本领域已知的一种或多种加氢处理催化剂的存在下,在温和条件下(优选地在液相条件下)进行加氢处理反应时,主要仅减少LWP中存在的二烯烃。用于二烯烃的选择性还原的示例性加氢处理反应条件包括温度120-210℃和压力1-50巴表压(barg)。示例性压力为28.5巴表压。液时空速(LHSV)通常为1-5h-1,优选地为4-4.5h-1。示例性的氢气/烃比(hydrogen/hydrocarbon ratio,氢气/烃的比率)是15N m3/m3。示例性的加氢处理催化剂包括NiMo和CoMo,优选地在载体上。示例性的加氢处理催化剂是NiMo/Al2O3。另一种示例性的加氢处理催化剂是CoMo/Al2O3。
将包含石脑油的二烯烃耗尽的馏出物进料至分离单元(如蒸馏单元C),其中将一种或多种馏分与底部馏分70分离,所述一种或多种馏分包含至少石脑油馏分50,其在大气压下沸点低于180℃。根据一个实施方式,蒸馏产生了在大气压下沸点低于180℃的石脑油馏分50和包含在大气压下沸点高于180℃的材料的底部馏分70。
根据另一个实施方式,蒸馏产生了在大气压下沸点低于180℃的石脑油馏分50,和在大气压下沸点在180℃和360℃之间的中间馏分60。根据该实施方式,底部馏分70包含在大气压下沸点高于360℃的材料。
根据一个实施方式,在大气压下进行蒸馏。根据另一个实施方式,在减压下进行蒸馏。根据另一个实施方式,在超压下进行蒸馏。
根据优选的实施方式,将石脑油馏分50进料至氢化处理单元D。优选地,使用NiMo-和CoMo-型催化剂进行氢化处理,其除去了石脑油馏分中剩余的杂原子,如氯、氧、硫和氮,并且同时对其中存在的烯烃和芳香族化合物实施氢化。石脑油的氢化处理通常在氢气的存在下,在升高的温度和压力下在气相中进行。示例性氢化处理反应条件包括温度280-350℃和压力20-100巴表压,优选20-50巴表压。LHSV通常为1-5h-1,并且氢气/烃比为100-900Nm3/m3,如360Nm3/m3。示例性的非限制性氢化处理催化剂是CoMo/Al2O3和NiMo/Al2O3。产物是氢化石脑油馏分80。
已知蒸汽裂化器对于进料的烯烃、芳香族化合物和杂原子含量具有规范。因此,氢化石脑油馏分80适合作为蒸汽裂化器E的进料。
LWP可以与炼油厂中的原油共处理。然而,由于来自原油蒸馏单元的产物通常导向非设计用于烯烃进料的单元,因此烯烃组分,并且具体地二烯烃的不存在将是有益的。上述限制在设计用于处理直馏石脑油的石脑油氢化处理单元的背景中特别相关。这些单元通常在气相中运行,并且由于化学反应所释放的热,发生在反应器内部的整体放热量(即温度升高)受到限制。将烯烃进料添加至这种反应器可以导致整体放热量显著增加,这进而可以缩短氢化处理催化剂的寿命。因此,还从精炼厂的角度,在精炼厂共处理前,从LWP除去石脑油馏分也是有益的。与石脑油馏分相比,在精炼厂对重LWP馏分的共处理问题较少,因为设计用于中间馏出物和例如重瓦斯油或真空瓦斯油的氢化处理单元另外还用于处理来自例如减粘裂化或延迟焦化单元的热裂化的进料。
根据特定实施方式,将底部馏分70与原油90,例如在混合单元F中混合以形成混合物100,然后将其进料至原油蒸馏单元G,其中混合物被分离成一个或多个蒸馏流110、120。
根据另一个实施方式,将中间馏分60与原油90,例如在混合单元H中混合以形成混合物,然后将其进料至原油蒸馏单元I,其中混合物被分离成一个或多个蒸馏流140、150。
根据另一个实施方式,将底部馏出物30与原油90,例如在混合单元J中混合以形成混合物160,然后将其进料至原油蒸馏单元H,其中混合物被分离成一个或多个蒸馏流170、180。
根据另一个实施方式,本发明涉及从包含二烯烃的LWP所产生的氢化石脑油作为蒸汽裂化器进料的用途。蒸汽裂化器进料是通过包括以下步骤的方法产生的:
a)提供包含二烯烃和石脑油的LWP流,
b)使LWP流经受蒸汽汽提塔以获得包含二烯烃和石脑油的馏出物、和底部馏出物,
c)使馏出物在氢气和一种或多种加氢处理催化剂的存在下经受加氢处理反应条件以产生二烯烃耗尽的馏出物,以及
d)将二烯烃耗尽的馏出物分离成
·一种或多种馏分,包含:至少石脑油馏分,在大气压下沸点低于180℃;和任选的中间馏分,在大气压下沸点在180℃和360℃
之间,和
·底部馏分,以及
e)使石脑油馏分在氢气和一种或多种氢化处理催化剂的存在下经受氢化处理反应条件。
本发明的方法适合于处理不同类型的液化废物聚合物以及它们的混合物,如废塑料热解油(WPPO)和水热液化的废塑料油。根据一个实施方式,液化废物聚合物包含WPPO。根据另一个实施方式,液化废物聚合物包含水热液化的废塑料油。
蒸汽汽提塔在处理LWP的方法中的使用具有以下优势
○减少塔中二烯烃引起的污染。
○蒸汽汽提将存在于LWP中的大部分金属积累在底部馏出物中,因此在石脑油中产生了低金属含量。这进而保护了二烯烃去除催化剂并延长其寿命。
○由于步骤b)的底部馏出物以及步骤d)的底部馏分和任选的中间馏分主要不含二烯烃,因此它们可以与原油混合并用作炼油厂中的进料。
在以上给出的描述中所提供的具体实例不应视为对所附权利要求的范围和/或应用性的限制。
Claims (19)
1.一种用于处理液化废塑料(LWP)的方法,所述方法包括以下步骤:
a)提供包含二烯烃和石脑油的LWP流,
b)使所述LWP流经受蒸汽汽提塔以获得包含二烯烃和石脑油的馏出物、以及底部馏出物,
c)使所述馏出物在氢气和一种或多种加氢处理催化剂的存在下经受加氢处理反应条件以产生二烯烃耗尽的馏出物,以及
d)将所述二烯烃耗尽的馏出物分离成
·一种或多种馏分,包含
○至少石脑油馏分,在大气压下沸点低于180℃,
○任选的中间馏分,在大气压下沸点在180℃和360℃之间,和
·底部馏分。
2.根据权利要求1所述的方法,包括
e)使步骤d)的所述石脑油馏分在氢气和一种或多种氢化处理催化剂的存在下经受氢化处理反应条件以产生氢化石脑油。
3.根据权利要求1或2所述的方法,其中,步骤b)的所述加氢处理反应条件包括温度120-210℃和压力1-50巴表压。
4.根据权利要求3所述的方法,其中,所述加氢处理反应条件包括LHSV 1-5h-1,优选4-4.5h-1。
5.根据权利要求1-4中任一项所述的方法,其中,所述一种或多种加氢处理催化剂选自CoMo和NiMo。
6.根据权利要求2-5中任一项所述的方法,其中,步骤e)的所述氢化处理反应条件包括温度280-350℃和压力20-100巴表压,优选20-50巴表压。
7.根据权利要求6所述的方法,其中,所述氢化处理反应条件包括LHSV 1-5h-1和氢气/烃比100-900Nm3/m3。
8.根据权利要求2-7中任一项所述的方法,其中,所述一种或多种氢化处理催化剂选自CoMo和NiMo。
9.根据权利要求2-8中任一项所述的方法,包括将所述氢化石脑油进料至蒸汽裂化器。
10.根据权利要求1-9中任一项所述的方法,包括将步骤d)的所述底部馏分与原油混合以形成混合物。
11.根据权利要求10所述的方法,包括将所述混合物进料至原油蒸馏单元。
12.根据权利要求1-11中任一项所述的方法,其中,步骤d)的所述一种或多种馏分包括在大气压下沸点在180℃和360℃之间的中间馏分。
13.根据权利要求12所述的方法,包括将所述中间馏分进料至原油蒸馏单元。
14.根据权利要求1-13中任一项所述的方法,其中,LWP选自废塑料热解油和水热液化废塑料油或它们的混合物。
15.根据权利要求1-14中任一项所述的方法,其中,LWP包括废塑料热解油。
16.根据权利要求2-8中任一项生产的氢化石脑油作为蒸汽裂化器进料的用途。
17.原油和步骤d)的底部馏分的混合物作为炼油厂进料的用途。
18.原油和步骤d)的中间馏分的混合物作为炼油厂进料的用途。
19.原油和步骤b)的底部馏出物的混合物作为炼油厂进料的用途。
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