CN1260237A - 以固定床进行放热反应的催化剂 - Google Patents
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Abstract
以固定床进行放热反应的催化剂,特别是乙烯氯氧化制备1,2－二氯乙烷的催化剂,其中包括由导热系数大于0.5W/cm/K的金属颗粒构成的惰性稀释剂。
Description
本发明涉及包含以固定床进行放热反应的催化剂的组合物，和用于减少和避免在固定床中形成过热点的金属稀释剂。
本发明尤其涉及其中的催化剂是乙烯氯氧化制备1，2-二氯乙烷的催化剂的组合物。
利用冷却流体排除放热反应的反应热，对于反应控制，并从而对于达到高转化率和高选择性的可能性是决定性的。
尽管在流化床操作中，由于在这些条件下可以达到高的总交换系数，这个问题是不重要的，但在固定床技术中，排除热量的问题是极其重要的，因为在床的入口处反应物的浓度高，因而反应速率和热量的生成也最高。因此催化剂床内的温度往往迅速升高，产生高温区(过热点)，就催化剂迅速钝化而言，高温会产生严重的问题，且由于副反应的增加，随后会造成选择性的丧失。考虑到在一定的冷却表面和一定的总交换系数下热交换量是受床内温度与冷却流体温度之差控制的，还考虑到在正常条件下，热交换速率是由所述的温度差决定的，所以只有在利用温差除去反应产生的所有热量时，过热点的温度才不会升高。
而在床的最后部分，反应的速率(和从而产生的热量)非常低，因此不会出现过热点。
通过对催化剂采取措施降低过热点的温度，可以采用二种方法；
-在反应物入口的催化剂床区域采用几乎是不活泼的催化剂：
-采用惰性固体稀释剂在所述的区域稀释催化剂。
迄今所用的稀释剂材料包括例如石墨、碳化硅、大孔碳、低表面积的氧化铝、二氧化硅和玻璃珠。
由于它们的导热系数低，这些稀释剂实际上不适合将热量从过热区传导到热交换器的器壁。
而且，还由于它们的导热系数低，这些稀释剂不足以将热量从过热点区域传导出去，过热点是由于催化剂和稀释剂混合不均匀，出现催化剂的浓度峰值形成的。
现已意外地发现，采用对反应物和反应产物呈惰性的导热系数高的金属作为稀释剂，不仅能提高产率和催化剂的选择性，并从而提高设备的生产能力，而且还能在出现催化剂失活和/或钝化问题的情况下，减轻或避免催化剂的失活和/或钝化。
特别是在乙烯氯氧化制备1，2-二氯乙烷的情况下，采用导热系数高的稀释剂，能以单段反应代替通常的多段反应。
在根据本发明的组合物中，可以采用的稀释剂是导热系数大于0.5W/cm/K的金属(在温度400K-1573K下，即相当于在1270-1000℃下的估计值)。
铜的导热系数(W/cm/K)在400K为3.93，在1573K为3.39；铝的导热系数值在400K为2.4，在800K为2.18；镍的导热系数值在400K和1200K分别为0.8和0.76；锌的导热系数在所考虑的温度范围内大于1。
下面是一些不能使用材料的导热系数的实例：氧化铝在673K为0.13W/cm/K，石墨在400K和1200K下分别为0.04和0.01；不锈钢在573K和973K下分别为0.19和0.25。
选择可在根据本发明的组合物中使用的金属，在应用它们的反应中，它们对反应物和反应产物基本上是呈惰性的。
优选的金属是铜，由于其导热系数和密度高，密度高每单位体积金属的热容量也高，所以它能首先吸收并随后迅速传导大量的热。
尤其是在要求化学惰性高的反应条件下，铝和镍也是适合使用的。
优选采用几何形状和尺寸与同它们混合的粒状催化剂相同的金属稀释剂。采用形状和尺寸与催化剂不同的稀释剂也是可能的。
优选的形状是每单位体积的稀释剂具有大表面面积和较高空隙率的形状。这样选择是为了有利于热交换和降低压力损失。
这些形状的实例是具有大孔径贯穿孔的圆筒形状和圆环形状。
圆筒形状的实例是在每个瓣上都有贯穿孔的多瓣形状和几何面积大的其它形状。
在美国专利5,330,958中报道了这种类型的形状(对催化剂和载体而言)，在此引入该专利说明书作为参考。
圆筒形状的尺寸一般为高3-10mm，直径5-10mm。
稀释剂的百分率是反应放热性能和反应动力学的函数。
按混合物的体积计算，可采用的适宜百分率为10-80％。
在反应物进口处采用含有金属稀释剂的催化组合物构成床。
也可采用沿床向下催化剂浓度逐渐增高的各种床层。
以适合采用根据本发明的组合物的固定床进行的放热反应的典型实例，是乙烯氯氧化制备1，2-二氯乙烷的反应。
其它反应的实例是：正丁烷氧化制备马来酸酐；邻二甲苯或萘氧化制备邻苯二酸酐；由甲烷制备合成天然气；由乙烯和乙酸制备乙酸乙烯酯和由乙烯制备氧化乙烯。
在所述的氯氧化反应的情况下，业已发现，除了产率和选择性较高的优点以外，采用根据本发明稀释的催化剂，能以进行单段反应代替现有工艺过程中通常进行的多段反应。
然而在通常采用的反应条件下，采用根据本发明稀释的催化剂，能使所述的条件最佳化，以便采用可能是最好的方式，在产率和选择性二个方面利用催化剂较高的性能。
可以用金属稀释剂稀释的催化剂，包括在以固定床进行放热反应中可以采用的所有催化剂。
就乙烯氯氧化制备1，2-二氯乙烷的催化剂而言，有代表性的和优选使用的催化剂是基于氯化铜或羟基氯化亚铜的催化剂，其中包括选自碱金属氯化物和/或碱土金属氯化物和任选的稀土金属氯化物的助催化剂。
这些催化剂是由惰性的多孔载体，特别是由表面积为50-300m2/g氧化铝载带的。
在文献中，特别是在欧洲专利申请EP-A-176432中详细地叙述了这种类型的催化剂，在此引入该专利申请的说明书作为参考。在欧洲专利申请EP-A-176432所述的催化剂中，在催化剂颗粒表面上的氯化铜浓度比在催化剂颗粒内部低。
提供以下的实施例只是为了说明本发明，而不是限制本发明的范围。
实施例
A)催化剂的制备
将300g氧化铝造粒，制成三瓣形的圆筒状颗粒，颗粒上具有三个等距离的贯穿孔，与圆筒的轴平行，将它们加热到450℃。然后用含9.33gCsCl的水溶液浸渍，再加热到500℃，保持1h。
分别制备含58.33g CuCl2 2H2O和12.45g KCl的水溶液(以成品催化剂的重量百分数表示，Cu含量为4％，K含量为2％)。为了容易溶解氯化物，以35％的水溶液形式，加入8g HCl。采用该溶液浸渍用CsCl预处理过的载体颗粒。
所得的催化剂在120℃下用炉子干燥一夜后备用。
B)对反应器的说明
采用内径26mm、高130cm的管式反应器考查采用不同材料稀释的催化剂的性能。反应器的结构材料是Ni200。该反应器装有循环油的恒温控制夹套和加入反应物的导管。
经过计量加入反应物(HCl、C2H4、O2和N2)，由质量流量计控制。
在反应器的出口冷却反应产物：将液体产物(EDC、未转化的HCl、氯化的副产物和反应水)收集在烧瓶中，而将不冷凝的产物(O2、N2、CO和CO2)，在计量和色谱分析后送往排气管。液体产物由水相和有机相二相组成，用分液漏斗将二相分离，称重和分析：对水相滴定盐酸，而有机相用色谱法分析，确定EDC的纯度。
反应物通常在温度210℃加入，使反应达到所选择的温度，在达到稳定不变的条件后，在1-2h内收集液体产物并对气体进行监测。
对比实施例1
将按上述方法制备的催化剂装入反应器中。按以下方法将其与石墨混合：
-将厚度50cm未稀释的催化剂层装入反应器的下部(靠近产品出口处)，所装的量为185.2g(等于270cc)；
-将催化剂(45.5g，等于64cc)与石墨(82.2g，等于96cc)混合，然后加入反应器的上部，高度约30cm，所制的混合物含40％(体积)的催化剂。
因此催化剂床的总高为80cm。热电偶的支撑套管在反应器中与反应器同轴配置。在所述的套管中按10cm的间距插入9个检测反应器温度的热电偶。借助于这些热电偶，可以获得反应器的温度分布，将所述的温度分布标绘成图1中的曲线。
采取样品确定操作性能，实验条件和所得的结果列于表1。
实施例1
采用的方法与对比实施例1相同。催化剂的用量也相同，唯一的差别是所用的稀释剂类型不同，所用的稀释剂是高7mm，外径6mm，内径5.6mm的铜环。稀释剂的用量(重量)为225.7g(96cc)。
实验结果示于表1，为了比较，图1的曲线也绘出了实施例1所得的温度分布。
采用铜作为稀释剂对操作性能的影响是明显的；由于过热点温度较低，活性(以盐酸的转化率表示)和选择性(由于减少了碳氧化物和氯化副产物的生成)显著提高。表1不变条件床高 cm 80生产能力(总) Nl/h 720压力 Ate 3油温度 ℃ 210线速度 cm/s 18.5接触时间 Sec. 4.3
注：EDC：1，2二氯乙烷
| mol比例 mol比例Cl/C O2/C2H4 | 过热点温度℃ | 转化率％HCl C2H4 | 选择性％(mol)EDC COX EC | EDC纯度％(mol) | |||||
| 对比实施例 | 0.3930.424 | 0.1870.201 | 370370 | 86.285.2 | 34.636.9 | 95.894.6 | 2.402.39 | 0.120.26 | 97.998.7 |
| 实施例1 | 0.4010.4250.430 | 0.1930.2020.207 | 304305305 | 89.889.390.3 | 36.538.439.3 | 98.798.096.0 | 1.251.251.31 | 0.020.160.16 | 99.999.399.3 |
EC：氯乙烷
Claims (13)
1.催化组合物，包括催化剂和金属稀释剂催化剂是粒状的，具有规定的几何形状，适合以固定床进行放热反应，金属稀释剂的几何形状和尺寸与催化剂的几何形状和尺寸相同或不同，其特征在于，在400K-1573K下稀释剂金属的导热系数值大于0.4W/cm/K。
2.根据权利要求1的组合物，其中金属稀释剂是铜。
3.根据权利要求1的组合物，其中的金属选自铝、锌和镍。
4.根据前述权利要求1-3的组合物，其中金属稀释剂是具有至少一个贯穿孔的圆筒状颗粒或圆环状颗粒。
5.根据权利要求4的组合物，其中圆筒状颗粒是瓣上具有贯穿孔的多瓣状的。
6.根据前述权利要求1-5的组合物，其中稀释剂的用量按组合物的体积计算，为10-80％。
7.根据前述权利要求1-6的组合物，其中采用乙烯氯氧化制备1，2-二氯乙烷的催化剂。
8.根据权利要求7的组合物，其中催化剂包括一种由惰性多孔载体介质载带的铜化合物。
9.根据权利要求8的组合物，其中催化剂包括一种铜化合物，选自氯化铜和羟基氯化铜，由表面积为50-300m2/g的氧化铝载带。
10.根据权利要求9的化合物，其中催化剂包括一种助催化剂，选自任选与稀土金属氯化物混合的碱金属氯化物和碱土金属氯化物。
11.一种以固定床进行放热反应的方法，其中采用根据前述权利要求1-10的催化组合物。
12.一种以固定床进行乙烯氯氧化制备1，2-二氯乙烷的方法，其中采用根据前述权利要求8-10的催化组合物。
13.根据权利要求12的方法，其中反应是以单段进行的。
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| ITMI99A000016 | 1999-01-08 | ||
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| CN115845854A (zh) * | 2022-11-28 | 2023-03-28 | 高潞空气化工产品(上海)能源科技有限公司 | 一种高导热性耐高温催化剂及其制备方法和用途 |
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| TWI341218B (en) | 2005-11-14 | 2011-05-01 | Oxy Vinyls Lp | Catalyst compositions and process for oxychlorination |
| ITMI20082333A1 (it) * | 2008-12-29 | 2010-06-30 | Sud Chemie Catalysts Italia S R L | Precursori di catalizzatori di ossiclorurazione dell'etilene a dicloroetano. |
| GB201017804D0 (en) * | 2010-10-21 | 2010-12-01 | Telecomm Res Inst | Catalyst system |
| TWI642481B (zh) | 2013-07-17 | 2018-12-01 | 東楚股份有限公司 | Catalyst system for the production of heterogeneous catalysts and 1,2-dichloroethane |
| JP2015098443A (ja) * | 2013-11-18 | 2015-05-28 | 東ソー株式会社 | １，２−ジクロロエタンの製造用触媒システム及びそれを用いた１，２−ジクロロエタンの製造方法 |
| WO2015080611A1 (en) | 2013-11-26 | 2015-06-04 | Infra XTL Technology Limited | Catalyst for direct production of isoparaffin-rich synthetic oil and method for preparing catalyst |
| KR102604873B1 (ko) | 2015-07-22 | 2023-11-23 | 바스프 코포레이션 | 아세트산비닐 단량체 생산을 위한 높은 기하학적 표면적 촉매 |
| CN111356524B (zh) | 2018-02-14 | 2022-03-15 | 株式会社Lg化学 | 催化剂填充方法和使用该方法制备丁二烯的方法 |
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| IT1274033B (it) * | 1994-04-05 | 1997-07-14 | Montecatini Tecnologie Srl | Catalizzatore in granuli per la sintesi di 1-2 dicloroetano e preprocedimento di ossiclorurazione a letto fisso dell'etilene che utilizza tale catalizzatore. |
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| IT1282267B1 (it) * | 1995-03-14 | 1998-03-16 | Montecatini Tecnologie Srl | Catalizzatori e supporti per catalizzatori ottenuti per pastigliatura |
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| BR0000021A (pt) | 2000-08-08 |
| EP1020222B1 (en) | 2004-10-20 |
| EP1020222A3 (en) | 2001-11-21 |
| IL133859A0 (en) | 2001-04-30 |
| CA2293983A1 (en) | 2000-07-08 |
| ITMI990016A1 (it) | 2000-07-08 |
| EP1020222A2 (en) | 2000-07-19 |
| US6593269B1 (en) | 2003-07-15 |
| NO20000101L (no) | 2000-07-10 |
| KR20000062434A (ko) | 2000-10-25 |
| ZA200000048B (en) | 2000-07-11 |
| TR200000067A2 (tr) | 2000-11-21 |
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