CN1296335C - 用于制造双酚类的催化剂的再生方法 - Google Patents
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Abstract
一种再生失活的磺化阳离子交换树脂催化剂的方法，它包括在约70-95℃的温度用含有约5-20重量%的水在酚中的酚-水混合物洗涤失活的催化剂。
Description
本发明的背景
本发明涉及有效制造双酚类的方法。具体地说，本发明的公开内容涉及一种再生通常用于制造双酚类中的离子交换催化剂的方法。
双酚类是被用于制备化学产品诸如双氧树脂和聚碳酸酯类的原料。它们通常是通过缩合酚类和酮类来制备的。2，2-双(4-羟基苯基)丙烷(也被称为双酚A，此后称其为BPA)是双酚类化合物中最重要的成员之一。众所周知BPA可通过在一种酸存在的条件下使丙酮(也称为二甲基酮，此后称其为“DMK”)和苯酚反应而生产出来。常常地，在反应中还使用另外的助催化剂。
有一些酸性催化剂可用于双酚生产工艺中。近年来，酸性阳离子交换树脂已经占优势地位，其中强酸性的磺化聚苯乙烯离子交换树脂是特别有用的。然而，这些酸性催化剂中有些已显示出快速失活的巨大倾向。有许多失活的可能的理由，包括催化剂被，例如，存在于反应进料液中的金属所毒化。另外，热扰动可能引起键连在树脂上的酸性功能基团的丢失。主要的因素是存在于双酚类中的焦油和其它反应副产物，它们在某些情况中会集结在催化剂珠粒的内部。置换催化剂是昂贵的，在不利条件下会需要大量劳动，并且产生的化学废弃物必须适当地处置。
一些先有技术中的方法是致力于防止催化剂中毒。日本专利公开6-92889(1994年4月5日授权给Nakawa等人)公开了一种通过缩合DMK和苯酚来生产BPA的方法，其中在DMK进料液中甲醇的浓度维持在10,000ppm以下，以防止催化剂中毒。美国专利No.5,777,180类似地公开了从反应物料流中除去烷基醇的方法，也是为了防止催化剂中毒。
其它方法是致力于再生失活的催化剂。授权给Mitsubishi的日本专利公开57-075146公开了用硫醇来处理失活的巯基吡啶基催化剂，同时授权给Chiyoda Corp.的日本专利83-23210公开了用含有巯基胺类的苯酚溶液来处理失活的催化剂。其它用来再生用于生产双酚A中的磺化离子交换催化剂的方法需要用有腐蚀性的试剂或溶液进行多步的洗涤操作。例如，专利公开No.36908(研究公开内容，1995年1月，第12页)讲授了一种四步的操作程序，包括用1-15重量百分数(Wt.％)的强碱洗涤后接着用1-15％的强酸洗涤。为了从强的阳离子交换树脂中除去发色体，美国专利No.4,443,635公开了用pH值大于大约8的水溶液进行洗涤，并包含大约10-70重量％酚的碱金属或铵盐。
温和的条件被报道在授权给Melby的美国专利No.4,051,079中，其中公开了再生失活的磺化的酸性阳离子交换树脂催化剂的方法，即用含有90％以上苯酚以及一种其pka值小于大约3的羧酸的水溶液苯酚溶液通过上述树脂。然而，使用羧酸显著使再生工艺复杂化，因为酸倾向于迁移到催化剂珠粒的内部，并且在把催化剂珠粒重新用于制造双酚之前必须把它除去。
虽然在双酚类生产中提出过这么多促进催化剂再生的方法，但无论如何在此领域仍保留着对适宜于大规模工业生产工艺中有效的、效率高的方法的需求。
发明概述
一种失活的磺化阳离子交换树脂催化剂的再生方法，包括用基本上由5-20重量％的水在酚中形成的酚-水组合物在大约70-95℃的温度下洗涤失活的催化剂，其中酚-水组合物的量为催化剂重量的大约5至大约50倍，并且重新循环一定时间长度以有效地再生这种催化剂。
上述以及其它特色和益处可经由本领域的技术人员通过以下的详尽说明、附图和所附的权利要求来评价和理解。
优选实施方案的详述
一种失活的磺化离子交换树脂催化剂的再生方法，它包括在70-95℃用催化剂重量的大约5至大约50倍的重新循环的酚-水组合物洗涤这种失活的催化剂，该酚-水组合物主要由大约5-20重量％的水在酚中的混合物组成的。把洗涤组合物重新循环通过失活的催化剂床允许用明显较低数量的洗涤组合物来有效地再生这种催化剂，从而对于工业规模的工艺导致明显的节省。
一般，这种催化剂是磺化的芳香族酸性树脂，它包含带有许多侧面磺酸基团的烃类聚合物。这种侧面磺酸基团典型地被2-4％的二乙烯基苯所交联。磺化的聚苯乙烯，聚(苯乙烯二乙烯基苯)共聚物以及磺化的苯酚甲醛树脂在这方面都是有用的。优选这种催化剂是用2-4％二乙烯基苯交联的磺化聚苯乙烯。一些磺化的聚苯乙烯树脂催化剂是市场有售的，例如由Rohm and Haas公司以商品名称Amberlyst 131或Amberlyt 131以及由Bayer Chemical Company以商品名称K 1131出售的产品。这种酸性树脂的交换容量优选至少为每克干树脂大约2.0毫当量(meq.)的氢离子(H+)。最优选交换容量为每克干树脂在约3.0至约5.5meq H+范围内。
也可以使用助催化剂，并且一般包含烷基硫醇诸如甲基硫醇、乙基硫醇和丙基硫醇。甲基硫醇是目前优选的助催化剂。
在再生失活的磺化离子交换树脂催化剂中适用的酚类与在制备双酚类时所使用的相同。有用的酚类在其相对于酚羟基的对位最好有一个活泼氢。这类酚可以被一个或多个烷基诸如较低级的烷基例如甲基、乙基或叔丁基，卤原子诸如氯原子或其它不会干扰羰基缩合反应的取代基所取代。示例说明的酚类包括邻位和间位甲苯酚；2，6-二甲基苯酚；邻位仲丁基苯酚；1，3，5-二甲苯酚；四甲基苯酚；2-甲基-6-叔丁基苯酚；邻位苯基苯酚；邻位和间位氯代苯酚；邻溴苯酚；和2，6-二氯苯酚。最优选的是苯酚。用于再生催化剂的苯酚可以和用于双酚合成中的苯酚相同或不同。优选再生时所用的苯酚与合成中所用的苯酚相同。
用于制备双酚类中的羰基化合物可以是醛类，但优选是酮类。具体的酮类包括丙酮，甲乙酮，甲基丙基酮，甲基乙烯基酮，以及特别是苯乙酮和环己酮。特别优选的是丙酮(DMK)。
酚/水混合物是在酚中包含有效数量的水，一般基于洗涤组合物的总量计算至少为大约5重量％。水存在的最大允许量是通过稍为低于使混合物不再有效的数量决定的，但可例行地按具体情况决定并结合苯酚的同一性来变化。方便的最大允许量基于洗涤组合物的总重量计算约为20重量％的水。当水的比例更高时，混合物在室温就不再是一相的。优选的比例为基于洗涤组合物的总重量计算含水约5至约17重量百分数。
与先有技术的讲授形成对照，特别是和授权给Melby的美国专利No.4,051,079形成对照，酚/水混合物其实不需要被酸化以使它有效。这导致更经济和有效率的操作，因为事实上已没有酸要从催化剂珠粒中除去，也防止了进一步的设备腐蚀和耗损。
可以使用任何高于酚/水混合物的凝固点和低于水的沸点的温度，虽然最好是把酚/水混合物的温度维持在大约70至大约90℃的范围内。
实际上，阳离子交换树脂是处于罐内大的催化剂床中的形式。最好是，在再生过程中催化剂能保留在它的位置上。按此，失活催化剂的再生包括使上述酚/水混合物通过失活的酸性离子交换树脂的床来和它接触。重要地，本发明人在此已经发现洗涤组合物的体积可以通过重新循环这种组合物而达到最小，而不会损害再生操作的效力。这样，所需酚/水洗涤组合物的总重量可限制在被洗涤的催化剂的重量的大约5倍至大约50倍之间，优选大约为被洗涤的催化剂重量的20倍至大约50倍之间。
为了保持酚/水混合物的用量，洗涤流出液的全部或一部份被重新循环。酚/水混合物通过树脂床的速率典型地在0至大约2重时空速(WHSV)范围内。使催化剂再生变得有效所需重新循环的速度和时间长度将依赖于污染的程度和催化床的构型，这可由本领域的技术人员很容易地确定。一般，重新循环可有效改进催化剂的活性(由正常操作条件下丙酮转化率的改进来测量)至少约4％，优选约6％，最优选可大于约9％。
树脂床预先的酚洗涤可供选择地用来增加再生的效力。这样做会除去一些焦油，并将减少所需酚/水混合物的总量。最后的酚洗涤可供选择地被用来干燥树脂并除去任何游离的酸性焦油。
具体说来，这种再生失活的磺化离子交换树脂催化剂的方法优选地包括用酚/水混合物进料到树脂床中并且在它从树脂床中出口时测量酚对水的比率。典型地，树脂床会从酚/水混合物中吸收水(水合)，所以在酚/水混合物从树脂床出口以后必须加进水份以维持酚/水混合物中所需的水量。然后混合物重新循环并再次进料到树脂床中。这一过程被重复，直到进入树脂床中的酚/水混合物中的水量与从树脂床流出的酚/水混合物中的水量相同，并且正是在酚/水混合物中所需的水量。
本发明将进一步用以下非限制性的实施例来阐明。
实施例1
在BPA生产工艺线上取出含有约30吨磺化聚苯乙烯催化剂的反应床体，该催化剂可以商品名称Amberlyst 131(Rohm and Haas公司的产品)从市场买到，当新鲜时的可滴定酸度为大约5毫克当量/克。这种BPA生产工艺使用3-巯基丙酸作为本体助催化剂并用4.5重量％的在苯酚中的丙酮作为反应物进料源。
为测定催化剂再生的效力，在70℃测定了新鲜催化剂流出液中产物(BPA)和丙酮的数量以及运行3天以后产物和丙酮的数量。然后通过在70℃以1.6WHSV的速率用酚/水混合物(含10重量％的水)洗涤树脂床24小时(没有重新循环)来再生催化剂。然后重新开始反应并测量流出液中BPA和丙酮的数量。结果列于下面的表1中：
表1
| 在流出液中的BPA，重量％ | 在流出液中的丙酮，重量％ | |
| 新鲜的催化剂 | 11.1-11.3 | 0.79-0.84 |
| 再生以前 | 8.9 | 1.37 |
| 再生以后 | 10.3 | 1.08 |
像可从表1中看到的那样，催化剂的再生作用导致产生的产物数量的明显改进。
实施例2-10
在实施例2-10的每个实例中，30克的催化剂床体像实施例1中所描述的那样从生产规模的催化剂床中取出，该催化剂已经运行超过6个月。这种催化剂在实验室规模的实验中被用来测定催化剂再生作用的效力。催化剂再生作用的效力是通过丙酮转化百分数(即转化为BPA的丙酮的数量/使用的丙酮的数量)来测量的。像可从表2中看到的那样，使用了各种变化了的再生条件。当使用重新循环时，包括了水合条件。实施例9和10使用新鲜的催化剂，没有应用再生作用的试样被用来作为对照试样。
表2
| 编号 | 催化剂试样 | 再生作用参数 | 水合条件 | 再生作用条件 | 再生前丙酮转化(％) | 再生后丙酮转化(％) | 丙酮转化％之差 | ||
| 重新循环否 | 水(重量％) | 温度(℃) | |||||||
| 2 | A131 | 否 | 10 | 70 | WHSV＝0.28；238小时 | 78.7 | 89.6 | 11.9 | |
| 3 | A131 | 是 | 10 | 95 | WHSV＝1.09.5小时 | WHSV＝0.3125小时 | 68.0 | 73.5 | 5.5 |
| 4 | A131 | 否 | 10 | 95 | - | WHSV＝0.3324小时 | 69.0 | 71.4 | 2.4 |
| 5 | A131 | 否 | 17 | 95 | - | WHSV＝0.2724小时 | 65.7 | 75.9 | 10.2 |
| 6 | A131 | 是 | 17 | 95 | WHSV＝1.012.5小时 | WHSV＝0.2724小时 | 68.6 | 78.2 | 9.6 |
| 7 | A131 | 是 | 5 | 95 | WHSV＝1.013小时 | WHSV＝0.3124小时 | 70.2 | 73.9 | 3.7 |
| 8 | A131 | 是 | 10 | 95 | WHSV＝1.012小时 | WHSV＝0.06120小时 | 71.8 | 80.1 | 8.3 |
| 9* | A-131FRESH | - | - | - | - | - | 88.4 | - | - |
| 10* | A-131FRESH | - | - | - | - | - | 91.1 | - | - |
*对照试样
参照上面的表2可以看出，带有重新循环的再生作用是一种高度成功的方法，能使丙酮转化％增加多达9.6％。
虽然已经显示和描述了优选的实施方案，但仍可对它做出各种修饰和替代而没有偏离本发明的精神和范围。按此，应该理解本发明的描述是说明性的，而不是限制性的。
Claims (7)
1.一种用于生产双酚类中的失活的磺化离子交换树脂催化剂的再生方法，它包括：
在约70至约90℃的温度把失活的离子交换树脂与一种酚/水组合物接触，该组合物中主要含有大约5至大约20重量％的水；并
重新循环酚/水组合物一段时间，以有效地使催化剂再生。
2.权利要求1的方法，它进一步包括在与酚/水混合物接触之前，先把失活的离子交换树脂与酚接触。
3.权利要求1的方法，它进一步包括在与酚/水组合物接触以后，把树脂与酚接触。
4.权利要求1的方法，其中的酚/水组合物包含大约5至大约17重量％的水。
5.权利要求1的方法，其中酚/水组合物的重量为所述树脂重量的大约5至大约50倍。
6.权利要求5的方法，其中酚/水组合物的重量为树脂重量的大约20至大约50倍。
7.权利要求1的方法，其中酚/水组合物与树脂接触时的流速在0至大约2WHSV范围内。
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| DE102009023551A1 (de) * | 2009-05-30 | 2010-12-02 | Bayer Materialscience Ag | Regeneration von sauren Ionenaustauschern |
| JP6644633B2 (ja) | 2015-08-07 | 2020-02-12 | Ｊｆｅケミカル株式会社 | ジシクロペンタジエン類変性フェノール樹脂の製造方法 |
| JP7025165B2 (ja) * | 2017-09-27 | 2022-02-24 | キヤノン株式会社 | 露光装置、搬送装置及び物品の製造方法 |
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| US4107218A (en) * | 1976-06-16 | 1978-08-15 | Union Carbide Corporation | Decoloration of bisphenol-A recycle stream with cation exchange resin |
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| JPS5242861A (en) | 1975-09-23 | 1977-04-04 | Union Carbide Corp | Method of decoloring recirculated bisphenolla with cation exchange resin |
| US4051079A (en) | 1976-06-22 | 1977-09-27 | Union Carbide Corporation | Regeneration of acidic cation exchange resin using acidified phenol-water mixture |
| JPS5775146A (en) | 1980-10-27 | 1982-05-11 | Mitsubishi Chem Ind Ltd | Method for regeneration of catalyst |
| JPS57153042A (en) | 1981-03-19 | 1982-09-21 | Teijin Chem Ltd | Polycarbonate resin composition |
| US4391997A (en) * | 1981-10-23 | 1983-07-05 | General Electric Company | Ion exchange catalyzed bisphenol process |
| US4443635A (en) | 1982-12-06 | 1984-04-17 | Shell Oil Company | Removal of color bodies in bisphenol production |
| US5008470A (en) * | 1989-11-30 | 1991-04-16 | Shell Oil Company | Process for preparing a bisphenol |
| JP3475960B2 (ja) | 1992-09-11 | 2003-12-10 | 出光石油化学株式会社 | ２，２−ビス（４−ヒドロキシフェニル）プロパンの製造方法 |
| DE4312038A1 (de) | 1993-04-13 | 1994-10-20 | Bayer Ag | Mehrfach regenerierbare Ionenaustauscherharze mit geringer Alkyl-SH-Gruppen-Belegung |
| PL169996B1 (en) | 1993-06-22 | 1996-09-30 | Inst Ciezkiej Syntezy Orga | Method of treating an ion exchange catalyst for use in bisphenol a synthesis processes |
| JP3753455B2 (ja) | 1995-06-01 | 2006-03-08 | 三菱化学株式会社 | ビスフェノールａ製造用触媒の再生方法 |
| EP0876319B1 (en) | 1995-12-19 | 2001-06-20 | Shell Internationale Researchmaatschappij B.V. | Improved process for the production of bisphenols |
| JP3810167B2 (ja) | 1996-12-18 | 2006-08-16 | 三菱化学株式会社 | ビスフェノールａ製造用触媒の再生方法 |
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| US20030017935A1 (en) | 2003-01-23 |
| KR20040004598A (ko) | 2004-01-13 |
| EP1385809A1 (en) | 2004-02-04 |
| TWI295282B (en) | 2008-04-01 |
| JP2004528173A (ja) | 2004-09-16 |
| CN1531518A (zh) | 2004-09-22 |
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