CN1058480C - 乙酸乙烯酯的制备方法 - Google Patents
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Abstract
提供了用于由乙烯、乙酸和含氧气体生产乙酸乙烯酯的一种外层浸渍催化剂。该催化剂在150℃的产率大于每升催化剂每小时661克乙酸乙烯酯，该催化剂的基本组成为：(1)一种催化剂载体，其粒径约为3至7毫米，孔体积为每克0.2至1.5毫升；(2)分布在催化剂载体颗粒1.0毫米厚最外层内的钯和金；(3)约3.5%至9.5%(重量)的乙酸钾。该催化剂的特征在于金与钯的重量比在0.60至1.25范围内。
Description
本发明涉及用来由乙烯、乙酸和含氧气体生产乙酸乙烯酯的改进的钯/金催化剂。
利用乙烯、乙酸和氧在含钯/金催化剂和碱金属助催化剂存在下于气相中一起反应来生产乙酸乙烯酯，是一种已知方法。催化剂组分通常是承载在诸如二氧化硅或氧化铝之类的多孔载体材料上。
在这些催化剂的早期实例中，钯和金都或多或少地在整个载体中均匀分布(例如参见美国专利3725680、3743607和英国专利1333449)。后来认识到这样做是不利的，因为在反应发生之前反应物不会大量扩散到载体内部，所以在载体内部的催化剂对反应不起作用。换言之，相当大量的钯和金从未与反应物接触。
为克服这一问题，设计了制造催化剂的新方法，以便制得活性组分浓集在载体最外层的催化剂(外层浸渍催化剂)。例如，英国专利1500167要求保护的催化剂中，至少有90％的钯和金分布在载体颗粒中距表面不超过颗粒半径30％的那一部分，而英国专利1283737则指出，用碱溶液，例如碳酸钠或氢氧化钠溶液，对多孔载体进行预处理，可以控制向多孔载体内部渗透的程度。
美国专利4048096叙述了另一种能制得特别有效的催化剂的方法。在该专利中，用包括以下步骤的方法生产外层浸渍催化剂：(1)用水溶性的钯和金化合物的水溶液浸渍载体，溶液的总体积为催化剂载体吸收容量的95％至100％；(2)将浸渍过的载体在碱金属硅酸盐的溶液中浸泡，使载体沉淀上不溶于水的钯和金化合物，碱金属硅酸盐的量应该是，在载体与碱金属硅酸盐接触12到24小时后溶液的pH为6.5到9.5；(3)用还原剂将水溶性的钯和金化合物转化为金属钯和金；(4)用水洗；(5)使催化剂与碱金属乙酸盐接触；(6)将催化剂干燥。采用这种方法，据说所得催化剂的比活性在150℃下测定可为每小时每克贵金属至少83克乙酸乙烯酯。
在美国专利4048096的第五栏中提到，上述方法最好用来制备每升成品中含1.65至3.3克钯和0.75至1.5克金的催化剂。对于密度例如为6 00克/升的典型二氧化硅载体，上述这些范围按重量百分数计相当于0.25％至0.5％和0.12％至0.22％，因此Au∶Pd的重量百分数比为0.1 6至0.75。碱金属乙酸盐的量据称在每升5至60克之间有效，优选每升25至35克，在乙酸钾的情形这相当于0.75％至9.2％(重量)，优选3.8％至5.4％。
美国专利4048096公开了该发明的六个实施例。所有这些实施例使用的催化剂，金与钯的重量比均在0.42至0.45范围内，金含量为每升2.1克或更少。所述的最有效的催化剂是实施例3的催化剂，其金含量为每升2.1克，金与钯的重量比为0.42，每升催化剂在150℃每小时生产610克乙酸乙烯酯。根据我们在研究中得到的数据，计算机对这一催化剂活性的预测值更高，为661。
现已发现，通过将金与钯的重量比确保在0.60至1.25范围内，可以得到150℃的产率超过每升催化剂每小时661克乙酸乙烯酯的外层浸渍催化剂。另外还发现，对于指定的金属承载量，通过确保催化剂中的乙酸钾含量在3.5％至9.5％(重量)的范围内，可以进一步提高产率。
这一发现是相当意外的，与美国专利4048096的说法相矛盾，该专利建议金与钯的重量比应小于0.5。
美国专利4087622也公开了外层浸渍催化剂。在该专利的第二栏第47-50行提到，金属金相对于金属钯和金总重量的百分数最好是约5％至约60％。这些数字相当于金与钯的重量比在0.05至1.5的宽广范围内，表明这一变量严格与否并不重要。另外，提到的碱金属乙酸盐含量范围很宽(1％至30％(重量))，而且只举例说明了乙酸钾含量3％的催化剂。实施例4-1至4-7显示了在固定的钯承载量下改变催化剂中金含量的影响，但是在很宽的钯承载量范围内没有任何迹象表明金与钯之比起关键作用。
本发明提供了一种外层浸渍催化剂，用以由乙烯、乙酸和含氧气体生产乙酸乙烯酯，所述催化剂在150℃下的产率大于每升催化剂每小时661克乙酸乙烯酯，该催化剂的基本组成为：
(1)一种催化剂载体，其粒径约为3毫米至7毫米，孔体积为每克0.2至1.5毫升；
(2)分布在催化剂载体颗粒10毫米厚最外层中的钯和金；
(3)约3.5％至约9.5％(重量)的乙酸钾，其中所述催化剂内金与钯的重量比在0.60至1.25范围内。
本发明催化剂的另一优点是对形成乙酸乙烯酯的高度选择性，其代价是有诸如二氧化碳这类副产物生成。
关于催化剂的组分，催化剂载体优选多孔二氧化硅、氧化铝、二氧化硅/氧化硅或二氧化钛，最优选的是多孔二氧化硅。载体的表面积应在100-800米2/克的范围。关于催化剂中的钯含量，以超过每升催化剂2.5克为宜，以便得到上面提到的高产率。对于钠含量约0.5％(重量)的典型催化剂，钯含量优选大于每升催化剂3.0克，更为优选的是大于每升催化剂3.9克，最优选的是在每升催化剂3.9至6.1克范围内。另一方面，金含量应以大于每升催化剂1.5克为宜，对于具有上述钠含量的催化剂，优选大于每升催化剂1.8克，更为优选的是大于每升催化剂的2.3克，最优选的是在每升催化剂2.3至7.6克范围内。最后，金与钯的重量比优选在0.7至1.05范围内，最优选的是0.85至1.05。
关于催化剂的乙酸钾含量，优选在5％至9％(重量)范围内，以得到最佳活性。
在本发明的一个实施方案中，业已发现采用金与钯的重量比等于或大于约0.9的催化剂，能显著减小不良副产物乙酸乙酯的含量。
本发明的催化剂可以方便地用英国专利1559540中详述的方法制备。在该方法的第一步，将载体用一种溶液浸渍，溶液中含有所需数量的钯和金的可溶性盐。这些盐的实例包括可溶性卤化物衍生物。浸渍溶液优选水溶液，所用溶液的体积相当于载体孔体积的95％至100％，优选98％至99％。
浸渍后，将湿的载体用选自碱金属硅酸盐、碳酸盐或氢氧化物的碱金属盐水溶液处理。所用碱金属盐的数量应该是，在溶液与被浸渍的载体接触12-24小时之后，在25℃测得的溶液的pH在6.5至9.5范围内，优选7.5至8。优选的碱金属盐是硅酸钠、碳酸钠和氢氧化钠。
在上述的处理过程中，据信钯和金的氢氧化物沉淀或结合在载体上。为了将这些物质转化成金属态，用还原剂(例如乙烯、肼、甲醛或氢)处理浸渍过的载体。如果使用氢，通常需要将催化剂加热到100-300℃以使还原完全。
在进行了上述步骤之后，用水洗涤还原过的催化剂，用所需数量的碱金属乙酸盐浸渍，然后干燥。
用上述方法制备的本发明催化剂通常含0.5％(重量)的钠，其中大部分来自沉淀剂。正如在另一篇专利申请中所详述的，这类催化剂的钠含量最好小于这一数值，以达到最佳的催化剂产率。用乙酸钾溶液洗涤或使用不含钠的试剂，可以减少催化剂的钠含量。
用本发明的催化剂制备乙酸乙烯酯时，通常是使乙烯、乙酸和氧或空气与催化剂样品，在100-200℃范围、优选140-180℃范围的温度和大气压至20巴范围的压力下接触。该过程通常以非均相方式进行，反应物处于气相，氧含量低于自燃极限。反应通常用过量的乙烯进行，而乙酸的数量则由露点来推定。反应后，用常规方法将乙酸乙烯酯分离和纯化。
现在参考以下实施例说明本发明。制备催化剂样品的通用方法
在此方法中只使用去离子水。步骤(1)：载体的浸渍
将15克高比表面积的球形二氧化硅载体(KA160-ex，SudChemie公司)加到8.7毫升Na2PdCl4和HAuCl4水溶液中。钯和金的配合物的用量应能达到所要求的钯和金在载体上的承载量。加入过程是以一次全部加入的方式完成的，将混合物轻轻摇动，直到溶液完全被吸收。浸渍后，将浸渍过的载体在室温下放置2小时。步骤(2)：沉淀
将18毫升硅酸钠水溶液快速加到浸渍过的湿载体上。上述的18毫升硅酸钠溶液(SMS)的浓度用以下公式确定：1.8×[(1摩尔SMS/摩尔Na2PdCl4)+(2摩尔SMS/摩尔HAuCl4)+(0.02毫摩尔SMS/克载体)]。将混合物间歇摇动15分钟，然后静置过夜。步骤(3)：还原
将黑色小球上的水相用85％水合肼溶液处理。水合肼的用量用下式确定：22.5×[(1摩尔N2H4/摩尔Na2PdCl4)+(1.5摩尔N2H4/摩尔HAuCl4)]。将混合物轻轻摇动，然后静置过夜。步骤(4)：洗涤
将含有少量悬浮黑色固体的水相倾析出，用约50毫升水将小球洗涤四次，每次洗涤后都进行倾析。将催化剂转移到装有活栓的玻璃柱中，然后再以大约每12小时/升的速度用水洗，直到用硝酸银溶液检验洗出液的氯离子时呈阴性。步骤(5)—(7)：干燥、乙酸钾的承载和最后的干燥
将催化剂在鼓风烘箱中于60℃干燥过夜，冷却，然后用所需数量的乙酸钾在8.7毫升水中的溶液浸渍。摇动混合物，直到所有液体都被吸收，然后再于60％将催化剂在鼓风烘箱内的不锈钢筛网上干燥。催化剂试验方法及结果
试验在7.8巴和150℃下进行，取2.5克粒径5-6毫米的催化剂小球，用30毫升1毫米的玻璃珠稀释，装入内径10-11毫米的不锈钢管中。催化剂在7.8巴下于氮或氦气流下在160℃加热3小时、然后于乙烯气流中在150℃加热10分钟进行活化。随后将乙酸蒸汽与乙烯混合，在催化剂上流过至少1小时。在进料气中逐渐加入21％的氧在氦中的混合物，同时维持催化剂床最高温度150℃。催化剂热点保持在150℃6小时，然后随着催化剂失活令温度下降。反应混合物的最终组成是乙烯∶乙酸∶氧∶氦＝53.1∶10.4∶7.7∶28.6，总气时空速为3850时-1。用联机气液色谱仪每隔1小时分析气相中的产物气流。
活性按每小时每升催化剂生产的乙酸乙烯酯的克数(时空产率，ST Y)计算，选择性按转化成产物的乙烯百分数计算。所有引用的数字均以在达到全氧含量20小时后测得的活性和选择性为根据。制备催化剂样品的另一种方法
以下是制备催化剂的另一种改进的方法。步骤(1)：载体的浸渍
使用与上面提到的同样方法。步骤(2)：沉淀
使用与上面提到的同样的方法，但是用氢氧化钠作为沉淀剂。氢氧化钠的用量用以下公式确定：1.8×[(2摩尔NaOH/摩尔Na2PdCl4)+(4摩尔NaOH/摩尔HAuCl4)+(0.04毫摩尔NaOH/克载体)]步骤(3)：还原
使用与上面提到的同样的方法。步骤(4)：洗涤
象上述一样，用水洗涤步骤(3)的产物，但在洗柱时用乙酸钾(5％)代替水。步骤(5)：干燥
将步骤(4)的产物在鼓风烘箱内于不锈钢筛网上在60℃下干燥过夜。
实施例1表明贵金属含量对催化剂活性及选择性影响的催化剂试验。
按照上述的第一种通用方法制备催化剂。改变贵金属的含量以构成一组为统计目的设计的实验。试验催化剂的组成由X射线荧光分析确定并列在表1。每种情形中乙酸钾的目标含量均为7.0％(重量)，相当于2.8％(重量)的钾。所得载体含有0.4％(重量)的钾，因此钾的总含量为3.2％(重量)。各试验中催化剂的用量在0.5至2.5克范围内变化，以便能在一系列的转化率下测定催化剂的活性和选择性。催化剂的钠含量约为0.5％(重量)。
采用的试验条件如前所述。反应物的总流量是使对2.5克催化剂进行试验时气时空速(GHSV)为3850小时-1。对于对更少量催化剂进行的试验，维持总流速而使GHSV发生变化。操作20小时后记录活性、选择性和氧转化率的测定结果，也列在表2内。
活性、选择性和转化率随催化剂组成和重量的变化与以下表达式符合得最好：式1： STY＝ey，其中：y＝6.76+0.40(Pd-0.82)+0.13(Au/Pd-0.81)
-0.57(Au/Pd-0.81)2-0.16(Cat Wt-1.5) R2＝0.95式2： 选择性 ＝100-ez，其中：z＝1.41-0.29(Au/Pd-0.81)+0.49(Au/Pd-0.81)2
-0.39(K-3.25)+0.10(Cat.Wt-1.5)-0.10(Cat.Wt-1.5)2
R2＝0.74式3：氧转化率＝ 24.5+10.0(Pd-0.82)+7.74(Pd-0.82)(Cat.Wt-1.5)
+1.97(Au/Pd-0.81)-14.1(Au/Pd-0.81)2+11.6(Cat.Wt-1.5)
R2＝0.96
上述表达式中所用的缩写是：Pd＝催化剂中钯的重量百分数：Au/Pd＝金与钯的重量比；Cat.wt＝催化剂的重量(克)；K＝钾的重量百分数；STY＝用每升催化剂每小时产出的乙酸乙烯酯克数表示的时空产率。相关系数R2表明与数据符合良好。
为了确定在恒定转化率下催化剂组成的影响，将式3变换成催化剂重量作为钯含量、金/钯比和转化率的函数。将有代表性的氧转化率30％代入此函数。然后用变换式3所得的重量函数替换式1和式2中的催化剂重量项，得到表示在恒定转化率下催化剂活性和选择性随金属含量变化的表达式。
图1显示了金/钯比对活性的影响，对选择性的影响则示于图2。这些曲线表明，增加催化剂的钯承载量和将金/钯比增加到最佳值0.9至0.95，可以提高催化剂的活性。将金/钯比进一步提高到此值以上会降低催化剂的活性。
增加金/钯比也提高了选择性。最后，由图3可见，金/钯比为0.9或更高的催化剂不生成或很少生成乙酸乙酯副产物。
表1
用来以钯含量和Au/Pd比模拟
STY、选择性和转化率的数据
| Pdwt％ | Auwt％ | Au/Pd | Kwt％ | Cat.Wt | STY 选择性 O2转化率(在20小时后测定) |
| 0.580.580.880.910.910.911.010.911.060.580.580.921.001.010.910.910.740.700.880.870.580.920.87 | 0.260.260.420.340.340.340.440.341.210.830.830.830.870.440.340.340.490.290.421.160.260.831.16 | 0.450.450.480.370.370.370.440.371.141.431.430.900.870.440.370.370.660.410.481.330.450.901.33 | 3.33.33.33.23.23.23.13.23.13.23.23.13.13.13.23.23.33.43.33.23.33.13.2 | 0.772.492.502.502.500.762.501.250.852.500.802.461.550.800.502.092.502.502.500.852.481.480.89 | 801 95.4 12.3602 94.5 30.0702 94.9 36.3654 93.8 33.9624 94.2 32.2835 95.2 12.7727 94.7 35.9747 94.7 19.0993 96.2 16.0592 95.4 28.6771 96.0 11.4760 95.4 35.1939 95.3 28.0991 95.1 15.7879 95.8 9.2709 94.0 30.7693 94.8 35.7644 95.2 32.2691 94.9 36.3916 96.0 14.5555 95.5 25.3937 96.2 26.6857 96.4 14.0 |
3.2％(重量)的钾大约等于7.0％(重量)的乙酸钾。
实施例2表明乙酸钾含量对催化剂活性和选择性影响的催化剂试验
按照上述的通用方法制备含有一系列乙酸钾含量的催化剂，作为一组为统计目的设计的实验的一部分。合成了一批催化剂，其中钯的目标承载量为0.9％(重量)，金/钯比为0.44。将目标含量为0、3％、5％、7％和9％(重量)的乙酸钾浸渍在同一批催化剂上。用X射线荧光分析法进行金属分析，结果列在表2。
采用上述的试验条件对催化剂进行评价。操作20小时后测得的活性(STY、克乙酸乙烯酯/小时。升催化剂)和选择性(以乙烯计的％)也列在表2。
活性的变化与下式符合得最好：
STY＝160.5KoAc-12.4KoAc2+147
R2＝0.998其中，KoAc＝实际的乙酸钾重量百分数。
相关系数的平方(R2)表明与数据符合良好。钾承载量对活性(STY)的影响示于图4。该图清楚地表明了能使催化剂活性提高的最佳乙酸钾承载量范围。在所研究的钾含量范围内发现选择性也增加。
表2
催化剂活性和选择性
| 乙酸钾的目标重量％ | X射线荧光分析乙酸钾重量％ | 实际的乙酸钾重量％ | STY 选择性(20小时时) |
| 03579 | 0.481.772.483.314.06 | 03.245.027.108.99 | 148 84.3539 93.2631 94.2677 94.0585 94.3 |
Claims (10)
1.一种制备乙酸乙烯酯的方法，该方法包括：使乙烯与乙酸在含氧气体存在下反应，反应在100至200℃范围的温度和外层浸渍催化剂存在下进行，其中所述催化剂的基本组成为：
(1)一种催化剂载体，其粒径为3至7毫米，孔体积为每克0.2至1.5毫升；
(2)分布在催化剂载体颗粒1.0毫米厚最外层内的钯和金；
(3)3.5％至9.5％(重量)的乙酸钾，其中所述催化剂中金与钯的重量比在0.60至1.25范围内。
2.权利要求1的方法，其中催化剂中金与钯的重量比在0.7至1.05范围内。
3.权利要求2的方法，其中金与钯的重量比在0.85至1.05范围内。
4.权利要求1的方法，其中催化剂的乙酸钾含量为5％至9％(重量)。
5.权利要求1的方法，其中催化剂的钯含量为每升催化剂大于3.0克，小于等于6.1克。
6.权利要求5的方法，其中催化剂的钯含量为每升催化剂3.9-6.1克。
7.一种制备乙酸乙烯酯的方法，该方法包括使乙烯与乙酸在含氧气体存在下反应，反应在100至200℃范围的温度和外层浸渍催化剂存在下进行，所述催化剂的基本组成为：
(1)一种催化剂载体，其粒径为3至7毫米，孔体积为每克催化剂0.2至1.5毫升；
(2)分布在催化剂载体颗粒1.0毫米厚的最外层内的钯和金；和
(3)3.5％至9.5％(重量)的乙酸钾，其中金与钯的重量比为0.9-1.25。
8.权利要求7的方法，其中催化剂的乙酸钾含量为5％至9％(重量)。
9.权利要求7的方法，其中催化剂的钯含量为每升催化剂大于3.0克，小于等于6.1克。
10.权利要求9的方法，其中催化剂的钯含量为每升催化剂3.9-6.1克。
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| JP07415592A JP3369209B2 (ja) | 1991-05-06 | 1992-03-30 | 酢酸ビニルを製造するための触媒および方法 |
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| CA002081937A CA2081937C (en) | 1991-05-06 | 1992-11-02 | Catalysts for alkenyl alkanoate production |
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| DE4323980C1 (de) * | 1993-07-16 | 1995-03-30 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
| DE4323978C1 (de) * | 1993-07-16 | 1995-02-16 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
| DE4323981C1 (de) * | 1993-07-16 | 1995-03-09 | Hoechst Ag | Palladium und Kalium sowie Cadmium, Barium oder Gold enthaltender Schalenkatalysator, Verfahren zu dessen Herstellung sowie dessen Verwendung zur Herstellung von Vinylacetat |
| CA2135021A1 (en) * | 1993-11-19 | 1995-05-20 | David J. Gulliver | Process for the preparation of catalysts for use in the production of vinyl acetate |
| US5466652A (en) * | 1994-02-22 | 1995-11-14 | The Standard Oil Co. | Process for the preparation of vinyl acetate catalyst |
| SG47363A1 (en) * | 1994-02-22 | 1998-04-17 | Standard Oil Co Ohio | Process for the preparation of fluid bed vinyl acetate catalyst |
| US6395676B2 (en) | 1994-02-22 | 2002-05-28 | The Standard Oil Company | Process for the preparation of fluid bed vinyl acetate catalyst |
| US5550281A (en) * | 1994-06-02 | 1996-08-27 | Cirjak; Larry M. | Fluid bed process for the acetoxylation of ethylene in the production of vinyl acetate |
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| US4048096A (en) * | 1976-04-12 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Surface impregnated catalyst |
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| EP0403950A1 (de) * | 1989-06-15 | 1990-12-27 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Vinylacetat |
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| CA747415A (en) * | 1966-11-29 | Sennewald Kurt | Process for the manufacture of vinyl acetate | |
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| CH534005A (de) * | 1968-02-01 | 1973-02-28 | Bayer Ag | Verfahren zur Herstellung eines Palladium und Gold enthaltenden Katalysators |
| JPS5136413A (en) * | 1974-09-10 | 1976-03-27 | Kuraray Co | Fuhowaesuteru no seizoho |
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1991
- 1991-11-18 US US07/793,131 patent/US5179056A/en not_active Expired - Fee Related
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1992
- 1992-03-30 CN CN92102172A patent/CN1058480C/zh not_active Expired - Fee Related
- 1992-03-30 DE DE69226626T patent/DE69226626T2/de not_active Revoked
- 1992-03-30 AT AT92302781T patent/ATE169520T1/de not_active IP Right Cessation
- 1992-03-30 ES ES92302781T patent/ES2118788T3/es not_active Expired - Lifetime
- 1992-03-30 EP EP92302781A patent/EP0569624B1/en not_active Revoked
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1500167A (en) * | 1974-06-27 | 1978-02-08 | Bayer Ag | Process for the preparation of vinyl acetate |
| US4048096A (en) * | 1976-04-12 | 1977-09-13 | E. I. Du Pont De Nemours And Company | Surface impregnated catalyst |
| EP0403950A1 (de) * | 1989-06-15 | 1990-12-27 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Vinylacetat |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69226626T2 (de) | 1998-12-24 |
| ATE169520T1 (de) | 1998-08-15 |
| EP0569624B1 (en) | 1998-08-12 |
| ES2118788T3 (es) | 1998-10-01 |
| EP0569624A1 (en) | 1993-11-18 |
| CN1076875A (zh) | 1993-10-06 |
| DE69226626D1 (de) | 1998-09-17 |
| US5179056A (en) | 1993-01-12 |
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