CN1263711C - α-烯烃低聚物的生产方法 - Google Patents
α-烯烃低聚物的生产方法 Download PDFInfo
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- CN1263711C CN1263711C CNB028189000A CN02818900A CN1263711C CN 1263711 C CN1263711 C CN 1263711C CN B028189000 A CNB028189000 A CN B028189000A CN 02818900 A CN02818900 A CN 02818900A CN 1263711 C CN1263711 C CN 1263711C
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/30—Catalytic processes with hydrides or organic compounds containing metal-to-carbon bond; Metal hydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
本发明公开了一种通过使α-烯烃在催化剂和有机溶剂存在下进行低聚反应来生产α-烯烃低聚物的方法,该方法包括将含有机溶剂的溶剂以线形或柱状压力流体的形式,从装在反应器的蒸气相部分的空间内的喷嘴喷到反应器的蒸气相部分的器壁上的步骤,以进行所述低聚反应,同时清洁反应器的蒸气相部分的器壁。在本发明的生产方法中,可以有效地防止聚合物沉积在反应器的蒸气相部分的器壁上,并长时间地稳定操作所述反应器。
Description
技术领域
本发明涉及一种生产α-烯烃低聚物的方法。更具体地说,本发明涉及通过使α-烯烃在催化剂和有机溶剂存在下进行低聚反应来生产α-烯烃低聚物的方法,其中有效防止了聚合物沉积在反应器的蒸气相部分的器壁表面上,由此使反应器可以长时间稳定操作。
背景技术
具有不饱和双键和约4至约24个碳原子的α-烯烃低聚物是有用的物质,广泛用作烯烃基聚合物的单体和各种高分子聚合物的共聚单体,以及用作增塑剂、表面活性剂等的原料。通常通过在齐格勒催化剂存在下,在溶剂中低聚乙烯来生产所述的α-烯烃低聚物。
但是,在所述低聚反应中,高分子聚合物副产物往往随时间的流逝沉积在位于反应器上部的蒸气相部分的器壁表面上。如果不除去沉积的高分子聚合物而继续进行所述低聚反应,所述聚合物会逐渐生长,并且该生长的聚合物最终将由于其重量的增加而落在反应溶液中。该落下并包括在反应溶液中的高分子聚合物将导致用于除去反应热的外循环型换热器的堵塞,不能泵送等。一旦发生这样的不利情况,就要求停止反应器的连续操作,并花费时间来除去沉积在反应器中的聚合物。
为了在聚合反应过程中(例如在生产丙烯腈-苯乙烯共聚物树脂、苯乙烯树脂或聚甲基丙烯酸甲酯的过程中)抑制聚合物沉积在反应器的蒸气相部分的器壁表面上,已知一种方法,其中将原料单体和溶剂的混合溶液喷雾到反应器的上部蒸气相空间中,以润湿反应器的蒸气相部分的器壁,并由此减少沉积到其上面的聚合物的量(日本专利申请特许公开号9-77806)。但是,该出版物没有详细提及所述喷雾方法,而仅是描述到,所述被喷雾的溶液保持在0-60℃的温度。
还已知一种技术,其中部分溶剂被雾化并供应到反应器的蒸气相部分,以增加溶剂在蒸气相部分的浓度,从而防止污垢沉积(日本专利申请特许公开号49-86478)。但是,该技术仅适用于有限的聚合物,例如聚丙烯腈。
发明内容
考虑到上述问题而完成了本发明。本发明的一个目的是提供一种通过使α-烯烃在催化剂和有机溶剂存在下进行低聚反应来生产α-烯烃低聚物的方法,其中有效防止了聚合物沉积在反应器的蒸气相部分的器壁表面上,由此使反应器可以稳定地长时间操作。
作为深入研究的结果,本发明人发现,通过将与在低聚反应中使用的相同溶剂以线形或柱状压力流体的形式,从装在反应器的蒸气相部分的空间内的喷嘴喷到反应器的蒸气相部分的器壁上,可以实现上述目的。基于这种认识完成了本发明。
因此,本发明提供了一种通过使α-烯烃在催化剂和有机溶剂存在下进行低聚反应来生产α-烯烃低聚物的方法,包括将含有机溶剂的溶剂以线形或柱状压力流体的形式,从装在反应器的蒸气相部分的空间内的喷嘴喷到反应器的蒸气相部分的器壁上的步骤,以进行所述低聚反应,同时清洁反应器的蒸气相部分的器壁。
附图简述
图1是一个示意图,显示了本发明的生产α-烯烃低聚物的方法中所使用的反应器的一个实例。
图2是实施例和比较例中使用的反应装置的示意图。
图3是实施例中使用的反应器的侧视图,显示了安装在其中的喷嘴的位置。
图4是实施例中使用的反应器的平面俯视图,显示了安装在其中的喷嘴的位置。
实施本发明的优选实施方案
在本发明的生产α-烯烃低聚物的方法中,作为原料的α-烯烃在催化剂和有机溶剂存在下的进行低聚反应。
在低聚反应中用作原料的α-烯烃不局限于特定的物质,包括例如C2-C4的α-烯烃,例如乙烯和丙烯。在这些α-烯烃中,乙烯是特别优选的。
作为催化剂,可以使用齐格勒催化剂和铬基催化剂。一般地,使用齐格勒催化剂是合适的。
更具体而言,作为合适的齐格勒催化剂,可以使用包含(A)过渡金属化合物,(B)有机铝化合物和(C)需要时使用的任选的第三组分的组合的催化剂体系。
作为过渡金属化合物(A),可以使用如下通式(I)所示的那些化合物:
MXxYyOz (I)
其中,M为锆原子或钛原子;X为选自氯、溴和碘的卤原子;Y为RO-、R2N-、-OCOR、-OSO3R、R-、-Cp(环戊二烯基),其中R为直链或支链的C1-C20烷基,或如下通式(II)所示的β-二酮根(β-diketonate)基团:
其中R1、R2和R3各自独立地表示氢原子、C1-C20烷基或C1-C20卤代烷基,前提条件是R1、R2和R3之一表示C1-C20卤代烷基;x、y和z各自表示0至4的整数,条件是(x+y+z)为4。
所述过渡金属化合物的具体例子包括:ZrCl4,ZrBr4,
ZrI4,ZrBrCl3,ZrBr2Cl2,TiCl4,TiBr4,TiI4,TiBrCl3,TiBr2Cl2,Zr(OC2H5)4,
Zr(OC2H5)2Cl2,Zr(O-n-C3H7)4,Zr(O-n-C3H7)2Cl2,Zr(O-iso-C3H7)4,
Zr(O-iso-C3H7)2Cl2,Zr(O-n-C4H9)4,Zr(O-n-C4H9)2Cl2,Zr(O-iso-C4H9)4,
Zr(O-iso-C4H9)2Cl2,Zr(O-tert-C4H9)4,Zr(O-tert-C4H9)2Cl2,Zr((CH3)2N)4,
Zr((C2H5)2N)4,Zr((n-C3H7)2N)4,Zr((iso-C3H7)2N)4,Zr((n-C4H9)2N)4,
Zr((tert-C4H9)2N)4,Zr(OSO3CH3)4,Zr(OSO3C2H5)4,Zr(OSO3C3H7)4,
Zr(OSO3C4H9)4,ZrCp2Cl2,ZrCp2ClBr,Ti(OC2H5)4,Ti(OC2H5)2Cl2,
Ti(O-n-C3H7)4,Ti(O-n-C3H7)2Cl2,Ti(O-iso-C3H7)4,Ti(O-iso-C3H7)2Cl2,
Ti(O-n-C4H9)4,Ti(O-n-C4H9)2Cl2,Ti(O-iso-C4H9)4,Ti(O-iso-C4H9)2Cl2,
Ti(O-tert-C4H9)4,Ti(O-tert-C4H9)2Cl2,Ti((CH3)2N)4,Ti((C2H5)2N)4,
Ti((n-C3H7)2N)4,Ti((iso-C3H7)2N)4,Ti((n-C4H9)2N)4,Ti((tert-C4H9)2N)4,
Ti(OSO3CH3)4,Ti(OSO3C2H5)4,Ti(OSO3C3H7)4,Ti(OSO3C4H9)4,TiCp2Cl2,
TiCp2ClBr,Zr(OCOC2H5)4,Zr(OCOC2H5)2Cl2,Zr(OCOC3H7)4,
Zr(OCOC3H7)2Cl2,Zr(OCOC4H9)4,Zr(OCOC4H9)2Cl2,Ti(OCOC2H5)4,
Ti(OCOC2H5)2Cl2,Ti(OCOC3H7)4,Ti(OCOC3H7)2Cl2,Ti(OCOC4H9)4,
Ti(OCOC4H9)2Cl2,ZrCl2(HCOCFCOF)2,ZrCl2(CH3COCFCOCH3)2等。
这些过渡金属化合物(A)可以单独使用,或者任何两种或多种组合使用。
作为有机铝化合物(B),可以使用以下通式(III)所示的那些化合物:
AlYaXbOcNd (III)
其中,X为选自氯、溴和碘的卤原子;Y为RO-、R2N-、-OCOR或R-,其中R为直链或支链的C1-C20烷基;a、b、c和d各自为0至3的整数,条件是(a+b+c+d)等于3,和/或
以下通式(IV)所示的那些化合物:
Al2Ya’Xb’Oc’Nd’ (IV)
其中,X为选自氯、溴和碘的卤原子;Y为RO-、R2N-、-OCOR、-RCOCR’COR”或R-,其中R、R’和R”各自为直链或支链的C1-C20烷基;并且a’、b’、c’和d’各自为0至6的整数,条件是(a’+b’+c’+d’)等于6。
上述通式(III)所示的有机铝化合物的例子包括:
Al(CH3)3,Al(C2H5)3,Al(C3H7)3,Al(iso-C3H7)3,
Al(C4H9)3,Al(iso-C4H9)3,Al(C5H11)3,Al(C6H13)3,Al(C8H17)3,Al(C2H5)2Cl,
Al(C2H5)2Br,Al(C2H5)2I,Al(C2H5)Cl2,Al(C2H5)Br2,Al(C2H5)I2,
AlC2H5(OC2H5)2,AlC2H5(OC3H7)2,AlC2H5(OC4H9)2,Al(OC2H5)2Cl,
Al(OC3H7)2Cl,Al(OC4H9)2Cl,Al(OC2H5)Cl2,Al(OC3H7)Cl2,Al(OC4H9)Cl2,
AlC2H5(OCOC2H5)2,AlC2H5(OCOC3H7)2,AlC2H5(OCOC4H9)2,
Al(OCOC2H5)2Cl,Al(OCOC3H7)2Cl,Al(OCOC4H9)2Cl,Al(OCOC2H5)Cl2,
Al(OCOC3H7)Cl2,Al(OCOC4H9)Cl2,Al(C2H5)2OC2H5,Al(C2H5)2OC3H7,
Al(C2H5)2OC4H9,Al(C2H5)2N(C2H5)2,Al(C2H5)2N(C3H7)2,Al(C2H5)2N(C4H9)2等。
上述通式(IV)所示的有机铝化合物的例子包括:
Al2(CH3)3Cl3,Al2(CH3)3Br3,Al2(C2H5)3Cl3,
Al2(C2H5)3Br3,Al2(C2H5)3I3,Al2(C2H5)3BrCl2,Al2(C3H7)3Cl3,Al2(iso-C3H7)3Cl3,
Al2(C4H9)3Cl3,Al2(iso-C4H9)3Cl3,Al2(C5H11)3Cl3,Al2(C8H17)3Cl3,
Al2(C2H5)2(CH3)Cl3,Al2(OC2H5)3Cl3,Al2(OC3H7)3Cl3,Al2(OC4H9)3Cl3,
Al2(OCOC2H5)3Cl3,Al2(OCOC3H7)3Cl3,Al2(OCOC4H9)3Cl3等。
这些有机铝化合物(B)可以单独使用,或者任何两种或多种组合使用。
另外,作为需要时使用的任选的第三组分(C),可使用选自硫化合物、磷化合物和氮化合物中的至少一种化合物。所述第三组分(C)有助于改善作为目标产物的α-烯烃低聚物的质量。
可用于本发明中的硫化合物无特殊的限制,只要它们是有机硫化合物。硫化合物的实例包括:硫醚,如二甲基硫醚、二乙基硫醚、二丙基硫醚、二己基硫醚、二环己基硫醚和二苯基硫醚;二烷基二硫化物,如二甲基二硫化物、二乙基二硫化物、二丙基二硫化物、二丁基二硫化物、二己基二硫化物、二环己基二硫化物和乙基甲基二硫化物;噻吩类,如噻吩、2-甲基噻吩、3-甲基噻吩、2,3-二甲基噻吩、2-乙基噻吩和苯并噻吩;杂环硫化合物,如四氢噻吩和噻喃;芳族硫化合物,如二苯基硫、二苯基二硫化物、甲基苯基二硫化物和甲基苯基硫;硫脲;硫化物如甲基硫化物、乙基硫化物和丁基硫化物,等等。
可用于本发明中的磷化合物无特殊的限制,只要它们是有机磷化合物。合适的磷化合物的实例包括膦,如三苯基膦、三乙基膦、三丁基膦、三丙基膦、三辛基膦和三环己基膦。
可用于本发明中的氮化合物无特殊的限制,只要它们是有机氮化合物。合适的氮化合物的实例包括有机胺,如甲胺、乙胺、丙胺、丁胺、戊胺、己胺、环己胺、辛胺、癸胺、苯胺、苄胺、萘胺、二甲胺、二乙胺、二丁胺、二苯胺、甲基苯基胺、三甲胺、三乙胺、三丁胺、三苯胺、吡啶和甲基吡啶。
在本发明中,在上述的各种硫化合物、磷化合物和氮化合物中,例如选自二甲基二硫化物、噻吩、硫脲、三苯基膦、三丁基膦、三辛基膦和苯胺等的至少一种化合物特别优选用作组分(C)。
本发明的低聚反应中使用的有机溶剂的例子包括:环烷属基烃如环己烷和萘烷,芳烃和卤素取代的芳烃如苯、甲苯、二甲苯、氯苯、乙苯、二氯苯和氯代甲苯,脂族烃如戊烷、己烷、庚烷、辛烷、壬烷和癸烷,和卤代烷烃如二氯乙烷和二氯丁烷等。在这些有机溶剂中,优选的是烃基溶剂。这些有机溶剂可以单独使用,或者以任何两种或多种的混合物的形式使用。
上述组分(A)、(B)和(C)相对于有机溶剂的各自混合比例如下:组分(A)的用量可以为通常每250ml有机溶剂0.01至5毫摩尔,优选0.03至1毫摩尔;组分(B)的用量可以为通常每250ml有机溶剂0.05至15毫摩尔、优选0.06至3毫摩尔;组分(C)的用量可以为通常每250ml有机溶剂0.05至20毫摩尔,并且在使用上述硫化合物作为组分(C)时优选为0.1至10毫摩尔,或在使用上述氮化合物或磷化合物作为组分(C)时优选为0.05至5毫摩尔。
还有,更优选控制组分(A)和组分(B)的混合比例,使Ai/Zr或Ai/Ti的摩尔比为1至15。
本发明的低聚反应通常可以在115至160℃的温度和2.94至8.82MPa·G的压力下进行。反应时间根据温度和压力而不同,因此不能限定到一个具体的范围。但是,在反应器中的停留时间通常为约10至约60分钟。
按照本发明生产方法得到的α-烯烃低聚物是具有4个或更多个碳原子,特别是4至18个碳原子的各种低聚物。α-烯烃低聚物的具体实例包括乙烯低聚物如1-丁烯、1-己烯、1-辛烯、1-癸烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯等。本发明生产的α-烯烃低聚物可以呈这些低聚物的任何两种或多种的混合物的形式。
在本发明的生产α-烯烃低聚物的方法中,一种含有低聚反应中使用的同样溶剂的溶剂,以线形或柱状压力流体的形式,从装在反应器的蒸气相部分的空间内的喷嘴喷到反应器的蒸气相部分的器壁上,和如果需要,喷到机械密封或搅拌器的旋转轴上,以进行所述的α-烯烃低聚反应,同时清洁反应器的蒸气相部分的器壁。更优选所述溶剂以柱状压力流体的形式喷射。所述柱状压力流体意味着所述溶剂被直线喷射,而不会散到周围。当所述溶剂以这种柱状压力流体的形式喷射时,所喷射的溶剂可确保到达目标位置。除了低聚反应中使用的同样有机溶剂外,所述含有低聚反应中使用的同样有机溶剂的溶剂还可以含有各种其它溶剂,除非所述低聚反应和本发明的目的由于使用这样的溶剂而受到不利影响。
在图1中,示意性地显示了本发明的生产α-烯烃低聚物的方法中所使用的反应器的一个实例。如图1所示,具有多个柱形喷嘴4的环3被安装在带有搅拌器2的反应器10的蒸气相部分。所述柱形喷嘴4具有能够将溶剂以柱状压力流体的形式喷到反应器的蒸气相部分的器壁1或机械密封5上的结构。附图标号6和7分别表示被喷射溶剂的入口管线和反应溶液的液位。
在本发明中,为了确保使被喷射的溶剂到达器壁表面或机械密封,各喷嘴的尖端与溶剂将被喷射到的部分间的距离优选为20cm或更小。反应压力通常高达约2.94至约8.82MPa·G,使得所述蒸气相部分的蒸气密度非常高。因此,如果被喷射的溶剂不是呈柱状压力流体的形式和各喷嘴的尖端与溶剂将被喷射到的位置间的距离大于20cm,被喷射的溶剂可能不能到达目标位置。
另外,从好的清洁效果的观点看,被喷射的溶剂优选具有110℃或更高的温度,并且从喷嘴喷出的压力流体的压力优选比反应器内的压力高约0.3-1.0MPa。如果被喷射的溶剂的压力与反应器内的压力间的差小于0.3MPa,可能有被喷射的溶剂不能到达目标位置,由此不能得到足够的清洁效果的缺点。另一方面,即使所述压差大于1.0MPa,清洁效果不能被提高至相应于该大的压差的程度。
而且,在蒸气相具有沿反应器垂直方向的较长长度的反应器的情况下,例如通过以多级的方式提供各具有如图1所示的相同结构的多个环,可以提高所述蒸气相部分的下部器壁的清洁效果。
下面结合实施例更详细地描述本发明,但本发明决不局限于这些
实施例。
同时,使用图2中示意性显示的反应装置来进行下列实施例和比较例。
实施例1
(1)催化剂的制备
在氩气氛中,将250毫摩尔无水四氯化锆和2.5升干燥的环己烷加入配有搅拌器的5升瓶中,并将瓶中的物质在室温下搅拌10分钟。得到的混合物与三乙基铝[(C2H5)3Al]混合,然后与倍半氯化乙基铝[(C2H5)3Al2Cl3]混合。三乙基铝和倍半氯化乙基铝以这样的量使用,使(C2H5)3Al/(C2H5)3Al2Cl3的摩尔比为3.5,和[(C2H5)3Al2Cl3+(C2H5)3Al]/ZrCl4的摩尔比为7。
加完所有组分之后,将所得混合物在氩气氛中,在70℃下加热搅拌2小时,以形成一种络合物并制备出催化剂溶液。将这样制备的催化剂溶液用干燥的环己烷稀释至100体积,并将其放到催化剂罐15中。
(2)乙烯的低聚
使用如图1示意性所示的装有一个用于除去热量的外循环环管的全混釜式反应器10(高度(H):0.3m;宽度(W)0.6m;内容积:约200升)连续地进行低聚反应。
从溶剂罐11经过泵12以500升/小时的流量,向反应器10中加入作为溶剂的环己烷。环己烷溶剂的流量由阀14控制。
环己烷溶剂通过加热器13被加热至135℃,然后从安装在环3上的喷嘴4喷出。所述喷嘴4由4个指向反应器器壁的喷嘴4a和1个指向机械密封的喷嘴4b构成。这些喷嘴4的安装位置如图1,3和4所示。图3是显示所述喷嘴安装位置的侧视图,图4是显示所述喷嘴安装位置的平面俯视图。另外,所述喷嘴4是能够以柱状压力流体的形式(即直线喷射而不会散到周围)喷射所述溶剂的类型。各喷嘴的尖端与溶剂将被喷射到的位置间的距离设定为11cm,并且在喷嘴处的压差为约0.5MPa。同时,在图3中,附图标号2’表示搅拌器的旋转轴。
从催化剂罐15经过泵16以40升/小时的流量,向反应器10中加入用环己烷稀释的催化剂溶液。当溶剂罐11和催化剂罐15内的液位降低到预定高度时,分别用环己烷和催化剂溶液适当地补充这些罐。
将高纯度的乙烯气体连续供应到反应器的液相中,使反应压力维持在6.4MPa·G。
在通过阀23控制反应器10的液位以将其中的反应溶液的体积保持恒定在120升的情况下,将反应溶液进料至闪蒸器24。在反应器10中的停留时间控制为约13分钟,以溶剂(环己烷)计。反应器10的内容物由两级搅拌桨以200转/分钟的旋转速度搅拌。斜叶桨用作上级的搅拌桨叶,涡轮桨用作下级的搅拌桨叶。
通过利用泵21使反应溶液循环通过安装在外循环环管中的管壳式换热器17(换热面积:10m2)来除去反应热。通过泵19和加热器20(在此水被加热至100℃),从水罐18向换热器17供应带压的水。供应到换热器的水被蒸发成蒸汽,从循环通过该换热器的反应溶液中除去热量,从而将反应器10内的温度保持恒定在130℃。通过阀22控制循环的反应溶液的流量,使在换热器17出口处的反应溶液的温度恒定地保持在125℃。
在连续操作720小时后,打开反应器10以检查是否有任何聚合物污垢沉积在反应器的蒸气相部分。结果证实,没有聚合物污垢沉积在蒸气相部分。
实施例2
按照实施例1同样的方式进行乙烯的低聚,只是将加热器13出口处的溶剂温度设定为120℃。
在连续操作720小时后,打开反应器10以检查是否有任何聚合物污垢沉积在反应器的蒸气相部分。结果证实,没有聚合物污垢沉积在蒸气相部分。
实施例3
按照实施例1同样的方式进行乙烯的低聚,只是将加热器13出口处的溶剂温度设定为100℃。
在连续操作720小时后,打开反应器10以检查是否有任何聚合物污垢沉积在反应器的蒸气相部分。结果证实,聚合物以薄膜的形式沉积在反应器的蒸气相部分的下部。
比较例1
按照实施例1同样的方式进行乙烯的低聚,只是使用完顶体喷嘴以圆锥形地和循环地喷射的方式来喷射溶剂,代替柱形喷嘴4。
在连续操作720小时后,打开反应器10以检查是否有任何聚合物污垢沉积在反应器的蒸气相部分。结果证实,约5mm厚的聚合物沉积在反应器的蒸气相部分的基本上所有表面上。
工业实用性
按照本发明的方法,当通过使α-烯烃在催化剂和有机溶剂存在下进行低聚反应来生产α-烯烃低聚物时,可以有效地防止聚合物沉积在反应器的蒸气相部分的器壁上,使得反应器可以长时间地稳定操作。
Claims (3)
1.一种通过使α-烯烃在催化剂和有机溶剂存在下进行低聚反应来生产α-烯烃低聚物的方法,包括将含有机溶剂的溶剂以线形或柱状压力流体的形式,从装在反应器的蒸气相部分的空间内的喷嘴喷到反应器的蒸气相部分的器壁上的步骤,以在115~160℃的温度和2.94~8.82Mpa的压力下进行所述低聚反应,同时清洁反应器的蒸气相部分的器壁,其中安装在反应器的蒸气相部分的空间内的喷嘴与反应器器壁间的距离为20cm或更小,其中被喷射的压力流体的温度为110℃或更高,其中所述α-烯烃是乙烯,并且所述有机溶剂是烃类溶剂。
2.权利要求1的方法,其中喷到反应器的蒸气相部分的器壁上的所述溶剂呈柱状压力流体的形式。
3.权利要求1的方法,其中所述催化剂是齐格勒催化剂。
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