CN86101398A - 聚合溶剂的净化方法 - Google Patents
聚合溶剂的净化方法 Download PDFInfo
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Abstract
一种适用于在齐格勒-纳塔(Ziegler-Natta)催化剂存在下进行烯烃聚合用溶剂的净化方法。该过程包括:将聚合溶剂通入一个多级蒸馏塔中烟囱式塔板下面的一级,烟囱式塔板要装在塔顶和塔底中间,有机铝化合物从高于烟囱式塔板的一级加入,冷凝液从烟囱式塔板抽出,经加热变成热蒸汽,再通入烟囱式塔板或高于烟囱式塔板但低于有机铝化合物进料的一级,净化的溶剂从塔顶抽出。
Description
本发明是关于聚合溶剂,特别是在齐格勒-纳塔(Ziegler-Natta)催化剂存在进行烯烃聚合用的溶剂的净化方法。
聚合溶剂,在其用于使用齐格勒-纳塔催化剂进行烯烃聚合之前进行净化是极其重要的,因为齐格勒-纳塔催化剂可被各种有毒组份,例如溶剂中含有的极性化合物作用而失去活性。因此,其净化一般要用一种具有专门精心设计的蒸馏塔在严格控制的操作条件下进行。实际上还要使用一种吸附剂,将溶剂中阻止聚合的组份吸附。
尽管上述蒸馏净化过程是一种可取的方法在此过程中阻止聚合的组份可为给定的,并其含量保持恒定,但是,如果所含的阻止聚合的组份不是给定的,或其含量变化的话,则不能达到要求的净化程度。
另一方面,该方法使用一种吸附剂,需要极高的操作,因为吸附剂和其本身用量相比吸附量极少,并且,当阻止聚合的组份浓度较高时,该方法不能处理大量的聚合溶剂。再者,该方法在工业规模实际应用中还有另一问题,那就是分析是否有一些阻聚组份与处理的溶剂混合比较困难。这样,一直希望开发一种简单而又经济的净化方法。
本发明的一个目的是提供一种改进的在齐格勒-纳塔催化剂存在下进行烯烃聚合使用的聚合溶剂的净化方法。
本发明另一目的是提供一种在齐格勒-纳塔催化剂存在下进行烯烃聚合使用的聚合溶剂的净化过程,通过该过程很容易除去聚合溶剂中阻聚组份。
本发明提出下述溶剂净化过程,所净化的溶剂适用于在齐格勒-纳塔催化剂存在下烯烃的聚合。
一种改进的聚合溶剂(这里所说的溶剂是指在齐格勒-纳塔催化剂存在下进行烯烃聚合使用的溶剂)蒸馏净化过程包括:
聚合溶剂从多级蒸馏塔的烟囱式塔板下面一级进入。所说的烟囱式塔板要装在塔顶和塔底之间;
有机铝化合物从烟囱式塔板上面一级进入;
冷凝液从烟囱式塔板抽出;
冷凝液加热变成热蒸汽;
热蒸汽通入烟囱式塔板或烟囱式塔上面,但在低于通入有机铝化合物的一级和净化的溶剂从塔顶排出,高沸物从塔底排出,从冷凝液中分出的高沸物从烟囱式塔板排出。
在附图中:
图1为适于实际采用的本发明蒸馏系统的具体过程。
图2为包括本发明过程的一种具体聚合过程的流程。
与本发明有关的齐格勒-纳塔催化剂对于熟悉该技术的人已为所共知。例如,在John Boor,Jr(Academic Press)所著“齐格勒-纳塔催化剂和聚合反应”,以及刊物“Macromolecular Seience-Reviews in Macromolecular Chemistry and Physics”c24(3),355~385(1984)和c25(1),57~97(1985)中这些催化剂均有所论述。本发明中可以用这种齐格勒-纳塔催化剂进行聚合的烯烃是那些最好有2~4个碳原子的烯烃,例如,乙烯、丙烯和丁烯-1。
对本发明使用的聚合溶剂没有特殊的限制,考虑到它与有机铝化合物的分离,聚合溶剂的沸点应在60-140°左右,例如,最好使用己烷、庚烷、辛烷、苯、甲苯、二甲苯、乙苯或它们的混合物。
这些聚合溶剂不仅包括从市场上可以买到的纯度较高的溶剂,而且包括从聚合系统回收的聚合溶剂。在使用从聚合系统回收的聚合溶剂时,使用本发明的方法进行净化,最好予先将低沸物,如未反应的单体,即乙烯、丙烯、丁烯-1和/或类似物除去之后再用。
尽管对本发明使用有机铝化合物没有特殊的限制,但是可以使用三烷基铝,例如,三乙基铝、三丙基铝或三异丁基铝;一囱二烷基铝,例如一氯二乙基铝或一氯二丙基铝;烷基铝倍半卤化物,例如三氯二乙基铝;二卤烷基铝,例如,二氯乙基铝;硫酸烷基铝或它们的混合物。
根据本发明关于上述有机铝化合物的加入量,如果已知阻聚组份,从烟囱式塔板向上流动加入为阻聚组份1-6倍(摩尔)的有机铝化合物则足够,如果不知阻聚组份,则必须改变其加入量,以找出阻聚组份不再向上流动的条件。换言之,即将从蒸馏塔顶收集的不含任何有机铝化合物的馏份与含有已知阻聚组份的聚合溶剂进行性能比较,以测定阻聚合组份和有机铝化合物的含量,然后,加入为阻聚组份量1~6倍(摩尔)的有机铝化合物。
按本发明方法,为使烟囱式塔板下面的塔板操作更有效,将塔顶排出的部分净化的溶剂通入塔顶下面紧邻的塔板和烟囱式塔板进行再循环,或从烟囱式塔板下面紧邻的塔板抽出部分蒸汽进行冷却,使蒸汽冷凝,然后将冷凝液进行再循环,均是可行的。
按本发明方法,这样一些阻聚组份可变成无害的,或者被转变成高沸物,因而不再上升到塔顶。从塔顶非常容易得到净化的聚合溶剂。另外,到达烟囱式塔板和塔底的阻聚组份均从蒸馏塔排出。因此,阻聚组份不需再经过任何进一步分解处理,以防止其向上流动到达塔顶。从而,本发明方法通过加入少量有机铝化合物很容易得到净化的聚合溶剂。本发明方法特别适于用做按上述方式工业规模制取净化的聚合溶剂的方法。
本发明及其效果在后面通过实施例和比较例进一步说明。下面给出的实施例只是为了说明,并不能看作对本发明的限定。
实施例1和比较例1-2:
用图1的蒸馏系统进行工业苯的净化。该蒸馏系统具有如下结构,其内径为40毫米,装有20级塔板。有机铝化合物进料管6通入第三级和第10级装有烟囱105形成烟囱式塔板(这样
,使冷凝液不会从第10级流下)。冷凝液排出管115与第10级连接。要净化的溶剂进料管111通入第17级塔板。再沸器102用于加热塔底液体。塔底装有塔底液体排出管114。冷凝液从冷凝液排出管115抽出,通过加热器103,进入蒸发器104。蒸发器104装有排出管112用于排出高沸物馏份。蒸汽进入管113通入第9级,从而将蒸汽从蒸发器104导入蒸馏塔。
另一方面,从塔顶出来的蒸汽,通过冷凝器106冷凝,部分冷凝液送入塔顶和第11级进行再循环,其余冷凝液通过管110作为净化的溶剂回收。
实施例1和比较例1-2均按下述操作进行。工业苯以30毫升/分流速通过进料管111。在实施例1中,通过进料管116以0.006毫升/分流速加入三乙基铝。在比较例1中,不加三乙基铝。高沸物馏份以0.2毫升/分的速度通过管114并以0.2毫升/分的速度通过管112排出,蒸馏塔的回流比为0.2,从塔顶得到29毫升/分的净化苯。
净化苯的分析
(A)催化剂浆液的制备
设有一个振动球磨机,装有两个容积为900毫升和内有80个钢球的球磨,钢球直径12毫米。每个磨中加入30克氯化镁,3毫升原醋酸乙酯和6毫升1,2-二氯乙烷。氯化镁研磨40小时。该过程重复进行两次。取80克这样研磨好的混合物,与500毫升四氯化钛一起,于2升园底烧杯中在80℃下搅拌2小时,使其静置,再除去生成的上清液。然后,加入1升正庚烷,搅拌15分钟。再使之静置,除去生成的上清液,这样洗涤重复7次,然后再加入500毫升正庚烷,配制成固体过渡金属催化剂浆液。
(B)聚合
使用上面配制好的过渡金属催化剂浆液进行聚合反应。在一容积为5升的高压釜中,加入30毫克上述过渡金属催化剂浆液,0.06毫升苯乙酸甲酯,0.128毫升一氯二乙基铝和0.08毫升三乙基铝。再加加有三乙基铝净化的苯样品(实施例1)作为稀释苯,另加不用三乙基铝净化的苯样品(比较例1)或工业苯(比较例2)作为稀释苯,加入量50毫升。稀释苯与高压釜内物料混合。然后,通入1.5公斤丙烯和1.5标准升(Nl)氢,在75℃下聚合两小时。然后,未反应丙烯放空,所得物料在减压下(20毫米汞柱)进行干燥(6小时),得到聚合物粉末。结果见表1。
实施例2和比较例3
(ⅰ)催化剂浆液的制备
取50升正庚烷,加入50克(以固体计)按实施例1方法制得的固体过渡金属催化剂浆液,214毫升一氯二乙基铝和100毫升苯乙酸甲酯,从而配成催化剂浆液。另外,在20升正庚烷中加入133毫升三乙基铝。
(ⅱ)聚合
利用附图2所示设备进行丙烯聚合。
按上述(ⅰ)制得的催化剂浆液和三乙基铝溶液,分别以3克/小时固体催化剂和8毫升/小时三乙基铝的速度,通过管13和14加入聚合反应器A中。反应器A的容积为500升。另外,加入80公斤/小时丙烯,在70℃下进行聚合。在聚合过程中,再加入正庚烷5升/小时,用于冲洗泵和阀门。
聚合反应器A中形成的含有聚丙烯的浆液,一部分用泵B以4800公斤/小时流量通过管15再循环回反应器A。另一部分含有聚丙烯浆液以80公斤/小时速度送入高压釜C(容积200升)。标有J、J′字母的是流量控制阀。通过管11向高压釜C中加入100毫升/小时二乙二醇-甲醚作为脱活剂。
含聚丙烯的浆液从高压釜C中放出,通过管16送至加热管D,在其中浆液进行加热。这样加热的浆液然后送至旋流分离器G中,将聚丙烯与正庚烷蒸汽分开。聚丙烯送至干燥器H中,将加热至90℃的丙烯通过管24进入干燥器H用于干燥聚丙烯,这样,通过管25则可得到30公斤/小时聚丙烯粉末。
从旋流分离G分出的蒸汽通过管17进入热交换器E,在此在0.1公斤/厘米2压力下被冷却到30℃,回收冷凝液,其中大部分为正庚烷。另一方面,从干燥器出来的含有丙烯的正庚烷在热交换器F中,在0.1公斤/厘米2表压下冷却到30℃,这样回收的冷凝液大部分亦为正庚烷。分别从热交换器E和F回收的冷凝液,其中主要组份为正庚烷,分别流经管19和20集中于储罐I中。收集速率为9.6升/小时。在热交换器E和F中未被冷凝的气体,分别通过管21、22,然后再经管23,送到丙烯回收系统(图中未划出)。
回收在储罐I中的冷凝液,主要组分为正庚烷,采用实施例1的同样方法净化。但净化的庚烷以5毫升/分的速度从塔顶抽出,然后经管117再回到蒸馏塔中。上升的蒸汽流量增加,和从塔顶抽出的净化庚烷稳定在29毫升/分,进行蒸馏。此外,在实例2中,通过改变三乙基铝进料量到0.008毫升而得到净化庚烷(回收液1),而在比较例3中,不加三乙基铝,从塔顶得到净化的正庚烷(回收液2)。
(ⅲ)按实施例1中(A)的同样方式,除了采用研磨混合物,加入量各为10克外,分别使用回收液1和2配制固体过渡金属催化剂。
(ⅳ)聚合反应
采用上述(ⅲ)方法制得的固体过渡金属催化剂进行聚合,并以按上述(ⅰ)方法制得的作为对比样。聚合反应按下述方式进行。就是说,将30毫克固体过渡金属催化剂、0.06毫升苯乙酸甲酯、0.128毫升一氯二乙基铝、0.08毫升三乙基铝和50毫升正庚烷〔两种催化剂均使用实施例1中(A)方法使用的正庚烷〕稀释剂组成混合物加入容积为5升的高压釜中,接着再加入1.5公斤丙烯和1.5标准升氢(Nl)。在75℃下进行聚合两小时后,将未反应的丙烯排出,剩下的物料在减压(20毫米汞柱)和60℃下干燥6小时,得到聚丙烯粉末。结果见表1。
实施例3和比较例4
用高活性三氯化钛“TGY-24(商品名,Marubeni-Solvay公司产品,组成为92%TiCl3和8%高沸点醚)作为固体过渡金属催化剂,在与实施例2的(ⅱ)方法中使用的同样设备中进行丙烯聚合。
为配制催化剂浆液,取100克上述三氯化钛、100升甲苯和800毫升一氯二乙基铝混合一起。向上述混合物中加入500克丙烯,在40℃下搅拌1小时,使每克三氯化钛聚合5克丙烯。然后加入0.5毫升二乙二醇-异丙基醚。得到予期催化剂浆液。然后,除了加7克/2小时这种催化剂浆液作为固体过渡金属催化剂和不加三乙基铝以外,均按实施例2中(ⅱ)的同样方式进行聚合。在聚合过程中,还要加甲苯以冲洗泵和阀门。冷凝液以12.8升/小时回收于储罐I中。
这样回收的冷凝液主要组成为甲苯,回收方式与实施例2中(ⅱ)方法相同,并作为回收液3(实施例3)和回收液4(比较例4)。在实施例3中,加入0.01毫升一氯二乙基铝作为有机铝化合物,但在比较例4中不加一氯二乙基铝。
每种这样回收的甲苯样品,各加100克/升三氯化钛催化剂,配成的混合物搅拌20小时。然后取这样配成的催化剂浆液进行聚合。加入由100毫克三氯化钛、0.8毫升一氯二乙基铝和100毫升甲苯(上述聚合使用的甲苯同样用于实施例3和比较例4)作为稀释剂组成的催化剂浆液,接着加入1.5公斤丙烯和3标准升(Nl)氢。之后在70℃下聚合3小时,用与上述实施例2中(ⅳ)同样的方法得到聚丙烯粉末。结果列入表1,
勘误表
补正:86101398 CPCH866088
Claims (7)
1、一种改进的聚合溶剂蒸馏净化过程,其特征在于所述的溶剂系用于在齐格勒-纳塔催化剂(Ziegler-Natta)存在下烯烃聚合,净化过程为:
将聚合溶剂通入多级蒸馏塔中烟囱式塔板下面的一级,烟囱式塔板安在塔顶和塔底之间;
有机铝化合物从高于烟囱式塔板的一级加入;
冷凝液从烟囱式塔板抽出;
冷凝液经加热变成热蒸汽;
热蒸汽通入烟囱式塔板或烟囱式塔板上面一级,但低于有机铝化合物进料的一级;和
从塔顶抽出净化的溶剂,从塔底排出高沸物,高沸物从烟囱式塔板出来的冷凝液分出。
2、如权利要求1所述的过程,在其中聚合溶剂的沸点为60~140℃。
3、如权利要求2所述的过程,其中聚合溶剂为己烷、庚烷、辛烷、苯、甲苯、二甲苯、乙苯或其混合物。
4、如权利要求1所述的一种过程,其中聚合溶剂用于聚合、并从中除去一种或一种以上未反应的单体。
5、如权利要求1所述的一种过程,其中有机铝化合物为三(低级烷基)铝、一卤二(低级烷基)铝、低烷基铝倍半氯化物、二卤低烷基铝、硫酸烷基铝或其混合物。
6、如权利要求1所述的一种过程,其中部分从塔顶抽出的净化的溶剂分别循环回紧接塔顶和烟囱式的塔板下面的一级。
7、如权利要求1所述的一种过程,其中蒸汽部分从紧接烟囱式塔板下面一级排出,经冷凝后,循环回到紧接烟囱式塔板下面一级中。
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JP60041867A JPS61203104A (ja) | 1985-03-05 | 1985-03-05 | 重合溶剤の精製方法 |
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CN1003858B CN1003858B (zh) | 1989-04-12 |
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US (1) | US4725338A (zh) |
JP (1) | JPS61203104A (zh) |
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CN (1) | CN1003858B (zh) |
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CN1935305B (zh) * | 2006-09-05 | 2010-05-12 | 上海兖矿能源科技研发有限公司 | 一种用于费托合成反应水中含氧有机物回收的精馏塔 |
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DE3832340A1 (de) * | 1988-09-23 | 1990-03-29 | Krupp Koppers Gmbh | Verfahren und vorrichtung zur optimierung des betriebes einer mit einem seitenkocher versehenen abtriebskolonne |
DE3942950A1 (de) * | 1989-12-23 | 1991-06-27 | Krupp Koppers Gmbh | Verfahren zur gleichzeitigen gewinnung von reinem benzol und reinem tuluol |
US5242549A (en) * | 1991-12-06 | 1993-09-07 | Shell Oil Company | Distillation separation process of titanium tetrachloride and halohydrocarbon |
US6790319B2 (en) * | 2000-12-01 | 2004-09-14 | Mitsui Chemicals, Inc. | Method for recovering titanium compound, process for preparing titanium halide, and process for preparing catalyst for polymer production |
KR20030088212A (ko) * | 2002-05-13 | 2003-11-19 | 재원산업 주식회사 | 메탄올 및 올쏘자이렌의 정제방법 |
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US3123591A (en) * | 1964-03-03 | Fractionation of polymerization diluent | ||
FR813164A (fr) * | 1937-07-06 | 1937-05-27 | Bataafsche Petroleum | Procédé de distillation |
US2374272A (en) * | 1937-08-21 | 1945-04-24 | Standard Oil Co | Olefin polymerization process |
FR984219A (fr) * | 1948-04-06 | 1951-07-03 | Bataafsche Petroleum | Procédé de séparation des hydrocarbures aromatiques par distillation extractive |
US2860126A (en) * | 1954-07-09 | 1958-11-11 | Phillips Petroleum Co | Polymerization process |
US2844569A (en) * | 1954-11-05 | 1958-07-22 | Exxon Research Engineering Co | Solution process for making isobutylene-diolefin synthetic rubber |
US2856392A (en) * | 1955-07-01 | 1958-10-14 | Exxon Research Engineering Co | Purification of polymerization diluents |
GB849232A (en) * | 1956-10-22 | 1960-09-21 | Phillips Petroleum Co | Method and apparatus for purification of solvent used in the polymerization of olefins |
US2943123A (en) * | 1958-09-26 | 1960-06-28 | Exxon Research Engineering Co | Polymerization diluent purification process |
US3129205A (en) * | 1958-11-03 | 1964-04-14 | Exxon Research Engineering Co | Reactor flushing system |
NL264682A (zh) * | 1959-09-23 | |||
US3153027A (en) * | 1960-01-21 | 1964-10-13 | Eastman Kodak Co | Process for removing impurities from recycle solvent for olefin polymerization |
US3655520A (en) * | 1969-03-06 | 1972-04-11 | Ethyl Corp | Distillation of olefins with alkanol addition to prevent degradation |
US3658780A (en) * | 1969-10-22 | 1972-04-25 | Phillips Petroleum Co | Polymerization of olefins |
BE759962A (fr) * | 1969-12-08 | 1971-06-07 | Exxon Research Engineering Co | Procede de polymerisation |
US3783126A (en) * | 1971-09-22 | 1974-01-01 | Stone & Webster Eng Corp | Fractionating hydrocarbons in a dual pressure fractionation tower |
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CN1935305B (zh) * | 2006-09-05 | 2010-05-12 | 上海兖矿能源科技研发有限公司 | 一种用于费托合成反应水中含氧有机物回收的精馏塔 |
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IN163530B (zh) | 1988-10-08 |
DE3606861C2 (zh) | 1988-09-01 |
FI81813C (fi) | 1990-12-10 |
AU564447B2 (en) | 1987-08-13 |
IT1204823B (it) | 1989-03-10 |
DE3606861A1 (de) | 1986-09-11 |
FR2578438A1 (fr) | 1986-09-12 |
GB8605283D0 (en) | 1986-04-09 |
FI860913A0 (fi) | 1986-03-04 |
PT82114B (pt) | 1987-12-30 |
AU5404686A (en) | 1986-09-11 |
KR860007313A (ko) | 1986-10-10 |
GB2173412A (en) | 1986-10-15 |
PT82114A (en) | 1986-03-01 |
IT8619615A0 (it) | 1986-03-04 |
CA1277945C (en) | 1990-12-18 |
KR890002558B1 (ko) | 1989-07-18 |
US4725338A (en) | 1988-02-16 |
FI860913A (fi) | 1986-09-06 |
FI81813B (fi) | 1990-08-31 |
JPS61203104A (ja) | 1986-09-09 |
FR2578438B1 (fr) | 1989-03-03 |
JPH0548243B2 (zh) | 1993-07-21 |
GB2173412B (en) | 1988-06-02 |
CN1003858B (zh) | 1989-04-12 |
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