CN1061904C - 双酚-a合成法用离子交换剂催化剂的处理方法 - Google Patents

双酚-a合成法用离子交换剂催化剂的处理方法 Download PDF

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CN1061904C
CN1061904C CN94106736A CN94106736A CN1061904C CN 1061904 C CN1061904 C CN 1061904C CN 94106736 A CN94106736 A CN 94106736A CN 94106736 A CN94106736 A CN 94106736A CN 1061904 C CN1061904 C CN 1061904C
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phenol
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CN1103396A (zh
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M·凯迪克
A·克鲁格
J·考特
Z·思维德斯基
A·考勒克
W·巴瑟维克
J·赫伯
M·马石扎克
J·尼兹拉
R·考思克
A·造德考
J·劳兹
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Blachownia Chemical Plant
Blachownia Organic Synthesis Institute
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4007—Regeneration or reactivation of catalysts containing polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/347—1,2-additions, e.g. aldol or Knoevenagel condensations via cationic intermediates, e.g. bisphenol A type processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Abstract

一种双酚-A合成法用离子交换剂催化剂的处理方法。该法包括含有0.01-2%(重)水的苯酚在50-90℃下洗涤阳离子交换剂床层；生成的含有40-99.5(重)苯酚和0.5-60%(重)水的洗液与碱性离子交换树脂接触；随后用蒸馏的方法除去水；经脱水的苯酚被循环，以便洗涤阳离子交换剂诃层；然后用含苯酚、丙酮、双酚-A、苯酚-丙酮缩合反应副产物和水的混合物在60-100℃下洗涤催化剂床层；洗液与碱性离子交换树脂接触，然后循环，以便洗涤阳离子交换剂床层。

Description

双酚-A合成法用离子交换剂催化剂的处理方法
本发明涉及一种酸性离子交换树脂形式的离子交换剂催化剂的处理方法，该催化剂用于双酚-A(2，2-二)4--羟苯基(丙烷)合成法中。
生成双酚-A和水的苯酚-丙酮缩合反应是在酸性离子交换树脂(阳离子交换剂)存在下进行。用于双酚-A制造法的阳离子交换剂是工业产品或用助催化剂改性以提高离子交换剂的催化活性和选择性的物类。在大多数情况下，离子交换催化剂的处理指的是将它们承载在助催化剂上。助催化剂也可用作反应混合物的组分。
纯化在双酚-A的生产中使用的离子交换剂树脂以便减少产物损失和提高其显色作用的方法也是大家熟悉的，两者都在由阳离子交换剂如磺酸化的苯乙烯-二乙烯基苯共聚物释放的低分子量磺酸存在下进行。
根据EP0324080，离子交换剂催化剂的处理要点是阳离子交换剂首先与碱如1-20％氢氧化钠水溶液接触，然后与强酸如2-10％硫酸水溶液接触，每一毫当量要中和的磺酸使用2-5毫当量的强酸。在这些操作过程之间，以及处理完成时，用水洗涤阳离子交换剂。这一处理离子交换剂催化剂的方法的缺点是生成大量含有无机盐的废液。其他已知的稳定产品显色作用的方法要点是在生产双酚-A的过程中，使用碱性离子交换树脂，在回收最后的产品以前，各种含有双酚-A的工艺物流都与碱性离子交换树脂接触。这样的解决办法的缺点在于，如果阴离子交换剂释放出胺类，生成产品的质量会受到损害。
本发明的目的是开发一种处理双酚-A合成法用离子交换催化剂的方法，它可降低生成的产品中的硫含量，而又不必经常地在双酚A制造过程中使用阴离子交换剂。已经知道在产品中硫含量的增加对其颜色稳定性有不良影响。
意想不到的是，发现通过在一定温度下用苯酚和特定组成的液体混合物与湿的阳离子交换剂接触，然后再与阴离子交换剂接触并循环回阳离子交换剂处理过程的方法处理的湿阳离子交换剂，当用作双酚-A合成法的催化剂时，可得到确实有更低硫含量的产品。
本发明的要点是在50-90℃的温度下用水含量为0.01-2％(重)的苯酚洗涤湿阳离子交换剂，它是磺酸化的苯乙烯-二乙烯基苯共聚物形式的酸性离子交换树脂。生成的含有40-99.5％(重)苯酚和0.5-60％(重)水的洗液然后与碱性离子交换树脂接触，然后用蒸馏的方法从洗液中除去水，脱水的苯酚循环以便洗涤阳离子交换床层，最后得到水含量不大于15％(重)的阳离子交换剂。然后阳离子交换剂床层在60-100℃的温度下用含有35-80％(重)苯酚、0.5-5％(重)丙酮、5-30％(重)双酚-A、0.5-30％(重)苯酚-丙酮缩合反应的副产物和0.1-3％(重)水的混合物洗涤，洗液再与碱性离子交换树脂接触，并循环以便洗涤阳离子交换剂。继续离子交换剂催化剂的处理，直到得到阳离子交换剂的水含量不大于5％(重)。
用本发明的方法进行处理时，阳离子交换剂当用于双酚-A合成法时，由于阴离子交换剂用于处理离子交换剂的过程中，而不是用于制备双酚-A的过程中，能得到硫含量低数倍的产品，同时不含任何游离的胺类。
实施例1-7
将200毫升有预定水含量的氢型磺酸阳离子交换剂放在装有加热套的玻璃柱(直径25毫米)中，并直接与另一玻璃柱(直径15毫米)相连，它也有加热套，并装填有50毫升Amberlyst A-21，一种有叔胺形式官能基的强碱性离子交换树脂形式的阴离子交换剂。通过液流流向柱K1来进行阳离子交换剂的处理，液流在受控的流速和温度TK1下向下流，首先通过柱K1中的阳离子交换剂床层，然后在温度TK2下通过柱K2的阴离子交换剂床层。含有0.1-0.2％(重)水的液体苯酚开始用来洗涤阳离子交换剂床层；洗液在循环到阳离子交换剂处理过程以前先用蒸馏的方法脱水。然后让含有苯酚、丙酮、双酚-A、丙酮-苯酚缩合反应的副产物和少量水的液体混合物通过柱K1和K2循环(实施例2-7)。在对比实施例中，只用苯酚处理阳离子交换剂。在处理过程中每隔一段时间测定阳离子交换剂的水含量。
经处理的阳离子交换剂用作双酚-A合成的催化剂。将70毫升处理过的阳离子交换剂和400毫升含有苯酚和丙酮的混合物(摩尔比为7∶1)装入安装有温度计、回流冷凝器和磁搅拌器的500毫升玻璃烧瓶中，随后在80℃下进行5小时双酚-A合成。通过从反应后混合物中直接结晶的方法回收苯酚-A加合物，然后在简单的真空蒸馏装置中在50毫米汞柱真空下进行分解，同时蒸出分离出的苯酚。分析得到的粗双酚-A，测定其硫含量。阳离子交换剂处理的物种、处理过程参数、阳离子交换剂的水含量和粗双酚-A的硫含量列入表1。用于处理阳离子交换剂的各物流的比较列入表2。
                                                                   表1
实施例        阳离子交换剂 用于阳离子交换有表2所示组成的物流编号 通过柱K1和K2的液体流速〔分米3/小时〕 柱内的床层温度〔℃〕 阳离子交换剂的水含量〔％(重)〕 粗双酚-A中的硫含量〔ppm〕
名  称   DVB％ To To   用液体流处理前   用液体流处理后
1(对比) Amberlyst-31   4    1     0.2   60     50     61.1     4.5   5.1
2 Amberlyst-31   4   14     0.20.2   5070     5060     63.113.6     13.64.1   0.3
3 Amberlyst-32 2   25     0.30.3   8060     7070     82.214.9     14.94.8   0.6
4 Wofatit FK-8   8   14     0.40.4   6080     6080     54.312.8     12.83.9   0.5
5 Amberlyst-15   20   23     0.10.1   7070     6050     52.113.4     13.42.6 0.7
6 Amberlyst-36 12   13     0.50.5   90100     90100     58.014.3     14.32.8   0.8
7 AmberlystXN1010   50   16     0.20.2   6070     5060     22.710.6     10.61.9   0.5
                                          表2
在表1所列的条件下用于处理阳离子交换剂的物流编号                        物流组成，％(重)
    苯酚     丙  酮     双酚-A     副产物     水
    123456     99.998.077.554.636.680.5     --0.82.83.54.8     --7.618.528.713.7     --13.322.728.40.8     0.12.00.81.42.80.2

Claims (1)

1.一种双酚-A合成法用离子交换剂催化剂的处理方法，其中用含有0.01-2％(重)水的苯酚在50-90℃下洗涤含有2-50％二乙烯基苯的磺酸化的苯乙烯-二乙烯基苯共聚物形式的酸性离子交换树脂作为氢型的阳离子交换剂床层，其水含量高达85％(重)，生成的含有40-99.5％(重)苯酚和0.5-60％(重)水的洗液与碱性离子交换树脂接触，随后用蒸馏的方法除去水，经脱水的苯酚被循环以便洗涤阳离子交换剂床层，以得到阳离子交换剂的水含量不大于15％(重)，然后用含有35-80％(重)苯酚、0.5-5％(重)丙酮、5-30％(重)双酚-A、0.5-30％(重)苯酚-丙酮缩合反应副产物和0.1-3％(重)水的混合物在60-100℃下洗涤催化剂床层，洗液与碱性离子交换树脂接触，然后循环，洗涤阳离子交换剂床层，以便得到阳离子交换剂的水含量不大于5％(重)。
CN94106736A 1993-06-22 1994-06-21 双酚-a合成法用离子交换剂催化剂的处理方法 Expired - Fee Related CN1061904C (zh)

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US6680270B2 (en) 2001-04-24 2004-01-20 General Electric Company Regeneration of catalysts used in the manufacture of bisphenols
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US6960697B2 (en) * 2002-03-13 2005-11-01 Mitsubishi Chemical Corporation System and method of producing bisphenol-A (BPA)
ES2383720T3 (es) * 2007-07-18 2012-06-25 Shell Internationale Research Maatschappij B.V. Método para el almacenamiento y/o transporte de bisfenolacetona y método para producir policarbonato aromático
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