CN1041967A - 低品位原料的分解处理方法及装置 - Google Patents

低品位原料的分解处理方法及装置 Download PDF

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CN1041967A
CN1041967A CN89107882A CN89107882A CN1041967A CN 1041967 A CN1041967 A CN 1041967A CN 89107882 A CN89107882 A CN 89107882A CN 89107882 A CN89107882 A CN 89107882A CN 1041967 A CN1041967 A CN 1041967A
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吉田雅彦
北山裕
饭田司
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Mitsui Chemical Industry Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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    • C10G55/00Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
    • C10G55/02Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means

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Abstract

本发明涉及低品位原料的分解处理方法和装置。将含大量重馏分的低品位原料从预热器中途抽送到气液分离器,将原料中的重馏分分离除去到必要程度后返回预热器,送热分解反应器进行热分解。因此大量重馏分造成的结焦、压力损失以及出口温度的上升等缺点都可以防止,从而可以进行长时期的连续运行。此外,通过调整过热稀释蒸气的加入量可以改变原料的蒸发率,控制重馏分的分离除去量,因而可充分处理产地不同的低品位原料。

Description

本发明涉及从含富高沸点馏分和蒸发残渣馏分等的重馏分的低品位原料中,分离除去上述高沸点馏分和蒸发残渣等重馏分来分解处理适于热分解用的低品位原料的方法及装置。
以前,在分解石脑油制取烯烃等的情况下,向分解石脑油的分解处理装置加入原料,全部在热分解炉对流部分的预热管蒸发,并在辐射部分的反应管进行热分解,然后再用骤冷式换热器冷却。以前所用的这种分解处理装置的结构如图3所示。在图中,分解处理装置60有热分解炉12和骤冷式换热器14及许多管。热分解炉12分为热分解炉对流部分18和热分解炉辐射部分20。在热分解炉对流部分18中,石脑油等原料a′由炉外的原料供给管34导入第一段预热器22,预热后,把预热的原料b′通过连接管62供给第二段预热器26,再次预热。预热过的原料b′在进入第二段预热器前,与由炉外经稀释蒸汽供给管44导入、并用稀释蒸汽过热器28过热的过热蒸汽c在连接管64处汇合而进行蒸发。
用第二段预热器26充分预热过的预热原料i′由连接管46送入热分解反应器30,进行热分解反应后,得到反应生成物j,并通入连接管48,在骤冷式换热器14中冷却后成为冷却生成物k,由生成物排出管50送往下面的工序。
这样的已有的分解处理装置60对于石脑油等品位高的分解原料是有效的分解处理装置。
然而,最近代之于以前的石脑油,必须用HNGL(由重质天然气液-气油田馏出气体时,伴随少量馏出的伴随油)等低品位原料作为分解原料。
在用这样的低品位原料作为分解原料的情况下,如果使用图3所示的现有石脑油等高品位原料的分解处理装置来热分解处理含富高沸点馏分和蒸发残渣馏分等重馏分的低品位原料,将会发生如下两方面的问题。
(1)在分解炉对流部分18的预热器22、26的管路内,特别是在蒸发完原料的预热器26的管路内,积累着蒸发残渣,生成所谓的结焦,妨碍流动,在短期内即可使设备不能连续运行。
(2)由于在热分解反应器30中生成大量易结焦物质,并在骤冷式换热器14中冷凝结焦而妨碍传热,进而使得骤冷式换热器出口温度及压力损失上升,造成不能连续地运行。
如上所述,低品位原料中的重馏分的存在,是温度为200~600℃的预热器管内和连接管及骤冷式换热器内结焦的原因,除了上述管路中的压力损失外,还会造成预热器管路以及骤冷式换热器出口气体的温度上升,从而出现短期后,设备即不能运行的问题。
因此,本发明的目的在于提供一种能够克服上述已有技术缺点的低品位原料的分解处理方法及装置,在含富高沸点馏分和蒸发残渣馏分等重馏分的低品位原料作为烯烃原料使用的情况下,把这样的高沸点馏分和蒸发残渣馏分等重馏分从热分解炉预热器中途抽出并分离除去,进行热分解,即使是低品位原料,也不仅能防止热分解处理装置各种管路,特别是连接管路内和预热器管路内结焦,还能防止进行骤冷的骤冷式换热器发生结焦,从而实现设备长时期的连续运行。
为了达到上述目的,本发明提供了一种低品位原料的分解处理方法,特征是在分解炉中分解处理含重馏分的低品位原料时,从上述分解炉的预热器中途抽出上述低品位原料,用气液分离方法从上述低品位原料中分离除去重馏分到必要的程度,例如到2-40%,此后,再使上述低品位原料返回上述预热器,并进行热分解反应。
此外,本发明还提供了一种低品位原料的分解处理方法,特征是在上述低品位原料的处理方法中,向由上述预热器中途抽出的低品位原料中通入必要量的过热稀释蒸汽,控制原料的蒸发率。
另外,本发明也提供了一种低品位原料的热分解处理装置,特征是在热分解处理含重馏分的低品位原料用的低品位原料热分解处理装置中,有由含至少第一预热器和第二预热器的热分解对流部分及设在热分解对流部分下游的含有热分解反应器的热分解辐射部分构成的分解炉,从上述低品位原料中除去上述重馏分用的气液分离器,与上述第一预热器相连的低品位原料供给管,与上述第一预热器和上述气液分离器相连接的管路,以及与上述气液分离器和第二预热器相连接的管路。
再者,本发明还提供了一种低品位原料的热分解处理装置,特征是在上述低品位原料热分解处理装置中,在上述气液分离器与第一预热器之间的连接管和/或上述气液分离器与第二预热器之间的连接管上连接有与供给过热稀释蒸汽用的稀释蒸汽过热管相连的管路。
图1是实施本发明低品位原料分解处理方法的分解处理装置简图。
图2是表示本发明实施例及比较例的骤冷式换热器出口温度与运行时间的关系的曲线图。
图3是现有技术的分解处理装置简图。
下面详细描述本发明的低品位原料的分解处理方法及装置。
本发明所用的低品位原料是含高沸点馏分和蒸发残渣馏分等重馏分的分解原料油,凡分解后能得到烯烃等的原料都行。例如作为最近的分解原料油而引入注目的HNGL(液化重天然气)等。HNGL是从天然气田馏出天然气时伴随少量馏出的伴随油。
所谓蒸发残渣馏分,是指在分解处理原料的分解炉的预热器内作为蒸发残渣留下来的馏分,高沸点馏分则是在预热器内虽被蒸发,但在分解反应后的骤冷式换热器冷凝时很容易生成高沸点物质的馏分。
本发明所用的低品位原料,不仅可以是含上述HNGL等重馏分的分解原料油,而且也可与石脑油等高品位原料以适当比例混合。
下面按照附图所示优选实施例详细说明本发明实施低品位原料分解处理方法的分解处理装置。
图1是分解处理装置的总体简图。如图所示,分解处理装置10主要具有热分解炉12和骤冷式换热器14,以及作为本发明特征的气液分离器16,及各种接管。
热分解炉12在上部有热分解炉对流部分18,在下部有热分解炉辐射部分20。在热分解炉对流部分18,从上部开始,设有管状的第一段预热器22,省热器24、管状的第二段预热器26、管状的稀释蒸汽过热器28。在分解炉辐射部分20设有反应管构成的热分解反应器30和分解炉加热用的燃烧器32。
在热分解炉对流部分18,低品位原料a从分解炉12外面供给第一段预热器22,原料供给管34与第一段预热器22的入口连接,预热器的出口与在分解炉12外面抽出的被预热的低品位原料b的抽出管36连接。抽出管36与由稀释蒸汽过热器28出口侧排出过热稀释蒸汽c的连接管38汇合,通入气液分离器16中。
在气液分离器16的上部,连接有输送分离出的气体原料e的送气管40。送气管40与由管38分出的支管39汇合,通入分解炉12内的第二段预热器26。另一方面,在气液分离器16的下部连接有排出分离出的重馏分g用的重馏分排出管42。
在稀释蒸汽过热器28的入口侧,连接有从分解炉12外面供给稀释蒸汽h用的稀释蒸汽供给管44。
热分解炉辐射部分20的热分解反应器30的入口经连接管46与第二段预热器26的出口相连接。热分解反应器30的出口经连接管48与分解炉12外的骤冷式换热器14相连接。
在骤冷式换热器14中,连接有送出回收冷却的烯烃等反应生成物用的生成物送出管50。
这里,第一段预热器22,预热上述含高沸点馏分和蒸发残渣馏分等重馏分的低品位原料a,第一段预热温度及压力虽然没有特别的限定,但该温度和压力最好应使得在热分解反应器30中反应时,用骤冷式换热器14冷凝时不易生成可结焦的物质的馏分充分蒸发,而仅仅在第二段预热器等管路中结焦,引起压力损失和温度上升馏分及热分解后容易生成可结焦物质的馏分不蒸发。这样的第一段预热温度及压力可按照低品位原料的种类、性质、气液分离器16、热分解炉12、特别是热分解反应器30及骤冷式换热器14的性能及操作条件合适地选定,例如,气液分离器的压力为2-12kg/cm2(表压),最好为3-7kg/cm2(表压),第一段预热温度是温度为150-350℃的预热器22的出口温度,最好是200-300℃。
如上所述,第一段预热后的低品位原料b,大量地含在热分解炉对流部分18的预热器26中作为蒸发残渣残留的馏分和分解反应后,在骤冷式换热器中容易生成可结焦物质的馏分,这些重馏分的沸点较高,例如在300℃以上,由于难于蒸发,重馏分即不要的部分大多存在于液相中。这种低品位原料b呈气液混合状态,例如气液比为气/液=60/40~98/2,优选70/30~95/5。将适量的过热稀释蒸汽c混入这种气液比的低品位原料b,调整气液比,作为调整低品位原料d送入气液分离器16,液相部分也就是含富高沸点馏分和蒸发残渣馏分等的液相重馏分g即和气相部分也就是基本上不含重馏分的气体原料e相分离。重馏分g在此由重馏分排出管42排出除去,而气体原料e由送气管40导出,与来自支管39的过热稀释蒸汽汇合,送入第二段预热器26。在该气液分离器16中,可从低品位原料分离除去重馏分到必要的程度,例如2-40%。
用第二段预热器26充分预热到不起分解反应的程度(700℃以下)。充分预热后的热气体原料i通过连接管46进入热分解反应器30,热分解反应完全后,反应生成物j通过连接管48送入炉外的骤冷式换热器14。
用骤冷式换热器14冷却后的反应生成物k由生成物送出管50送往下面的工序。
本发明方法的实施装置所用的预热器22和26可为管式预热器,但不限于此。
另外,省热器管24,只要能使预热器22与预热器26达到合适的预热温度都即可用。
再者,稀释蒸汽过热器28也没有特别的限定,但用管式过热器好。过热后的稀释蒸汽c能够促进HC(烃)的蒸发,调整预热低品位原料b的气液比。因此,通过调整向第一段预热后的预热低品位原料b的过热稀释蒸汽c的混合量,不但能够控制原料的蒸发率,防止重馏分造成管路等的结焦,还能充分地处理种类、特性,例如产地不同的低品位原料a,不必因产地不同而变更热分解处理装置的操作条件,也能极好地进行热分解。
用本发明的方法,可以根据造成重馏分含量等不同的产地差别自动控制过热稀释蒸汽量。
热分解反应器30可以采用管式热分解反应器,但不做特别的限定。
骤冷式换热器14也可以采用公知的类型,没有特殊的限定。
本发明的方法所用的气液分离器16,可以采用任何公知的类型,只要能把含重馏分g的液相部分与含气体原料e的气相部分合适地分离开即可。
下面,用具体实施例说明本发明的低品位原料分解处理方法及装置。
作为本发明的实施例,用图1中所示的热分解处理装置进行含富高沸点馏分和蒸发残渣馏分等重馏分的低品位原料的气液分离,除去5-20%的液体成分后,热分解处理时骤冷式换热器14的出口温度随运行时间的变化如图2所示。
作为比较例,用图3中所示的热分解处理装置,对与本发明实施例相同的低品位原料不分离除去重馏分即进行热分解处理时,骤冷式换热器14的出口温度随运行时间的变化也在图2中示出。
本发明的实施例及比较例的热分解处理条件,除去气液分离外,其它全部相同。
热分解处理条件:
低品位原料a        6.0大气压,15℃,30000kg/h
第一段预热温度        233℃
过热稀释蒸汽        4.8大气压,448℃
过热稀释蒸汽混合量:
预热低品位原料b:5000kg/h
气体原料e:8500kg/h
第二段预热温度        547℃
热分解反应温度        832℃
分离除去重馏分        3000kg/h
如图2所示,在本发明的实施例中,温度上升受到抑制,可以实现长期运行;相反,在比较例中,温度急剧上升,由于没有下降的趋势,所所以不能连续运行。
如上所述,利用本发明热分解处理含富高沸点馏分和蒸发残渣油等重馏分的低品位原料时,从热分解的预热器中途抽出上述低品位原料,第一段预热后,由于先分离除去上述的重馏分,然后再返回上述热分解炉,进行第二段预热后的热分解,能够防止分解处理装置各种管路和热分解炉、骤冷式换热器、特别是第一段预热器以后的管路等结焦。因此,能够防止上述分解处理装置的管路的压力损失,而且可以防止预热器管的温度上升,尤其是由于能够防止上述骤冷式换热器的出口温度上升,所以能够大大延长运行时间。
此外,利用本发明,由于进行低品位原料的二段预热,第一段预热后导入过热稀释蒸汽,在防止结焦的同时,还可以向上述低品位原料辅助供热。而且,改变其加入量,可以改变上述低品位原料的蒸发率,能够控制上述低品位原料中重馏分的分离除去量。为此,本发明可用同一处理装置,同样的处理条件,充分地处理产地不同的低品位原料。

Claims (4)

1、低品位原料的分解处理方法,特征是在分解炉中热分解处理含重馏分的低品位原料时,从上述分解炉的预热器中途抽出上述低品位原料,用气液分离方法从上述低品位原料中分离除去重馏分后,再使上述低品位原料返回上述预热器,并进行热分解反应。
2、权利要求1所述的低品位原料的分解处理方法,其特征是,向由上述预热器中途抽出的低品位原料中加入必要量的过热稀释蒸汽,由此控制原料的蒸发率。
3、热分解处理含重馏分的低品位原料的热分解处理装置,其特征在于,具有由含至少第一预热器和第二预热器的热分解对流部分以及设在上述热分解对流部分下游的含热分解反应器的热分解辐射部分构成的分解炉,还有从上述低品位原料中除去上述重馏分的气液分离器与上述第一预热器连接的低品位原料供应管,连接上述第一预热器和上述气液分离器的管路,以及连接上述气液分离器与第二预热器的管路。
4、权利要求3所述的低品位原料热分解处理装置,其特征是,在上述气液分离器与上述第一预热器之间的连接管和/或上述气液分离器与上述第二预热器之间连接管上连接有和供给过热稀释蒸汽用的稀释蒸汽过热管相连的管路。
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