CN103372452A - 乙苯脱氢制备苯乙烯的催化剂及其制备方法 - Google Patents
乙苯脱氢制备苯乙烯的催化剂及其制备方法 Download PDFInfo
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- CN103372452A CN103372452A CN2012101220777A CN201210122077A CN103372452A CN 103372452 A CN103372452 A CN 103372452A CN 2012101220777 A CN2012101220777 A CN 2012101220777A CN 201210122077 A CN201210122077 A CN 201210122077A CN 103372452 A CN103372452 A CN 103372452A
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Abstract
一种乙苯脱氢制备苯乙烯的催化剂及其制备方法。以催化剂质量为100份计,包括如下组份:a)45~75份K2Fe10O16;b)20~50份K2Fe22O34;c)1~12份的铈氧化物,以Ce2O3计;d)1~10份的钼和/或钨氧化物,以MoO3和/或WO3计;e)1~10份的钙和/或镁氧化物,以CaO和/或MgO计;其中K2Fe10O16与K2Fe22O34的质量比例为1.0~3.5∶1。该催化剂有较好的抗积炭能力和抗还原能力,具有良好的活性和稳定性,且使用寿命较长。
Description
技术领域
本发明涉及一种化工催化剂及其制备方法,具体来说本发明涉及一种用于乙苯脱氢制备苯乙烯的氧化物催化剂及其制备方法。
背景技术
目前,全球绝大多数的苯乙烯生产装置都采用乙苯催化脱氢技术生产,脱氢催化剂的发展已历经数代,由苯乙烯生产工业化初期使用的锌系、镁系催化剂发展到如今通用的铁系催化剂,其中含铬的铁系催化剂由于铬易造成环境污染而被淘汰,取而代之的是铁-钾-铈-钼系列。该系列催化剂一般采用干混-捏合-挤条-成型-干燥-焙烧的工序制备而成,其中通过高温焙烧的过程主要形成三种物相,即CeO2、α-Fe2O3和Fe2O3与K2O相互作用形成的铁酸钾KFeO2和/或KFe11O17晶相。大量的研究结果表明,铁酸钾是乙苯脱氢制苯乙烯催化剂中的主活性相和结构稳定剂。催化剂中形成该物相的含量越多,结晶程度越好,催化剂的活性也随之越高,稳定性越好。然而,在乙苯脱氢反应过程中会产生大量H2,使反应气氛具有很强的还原性,而铁在还原气氛下价态会由最初的三价转变成二价,从而破坏原有催化剂主活性相铁酸钾的结构,减少主活性相数目,最终导致催化剂失活。因此,对催化剂主活性相开展深入研究就成为研究该类催化剂使用性能稳定和延缓催化剂失活的关键之所在。
美国专利US6551958B1报导了基本组成为Fe-K-Ce-Mg的催化剂体系,该类催化剂的活性相包含一个或多个Fe/K相K2O∶Fe2O3=1∶n(其中n是从1到11的自然数),特别以K2O∶Fe2O3=1∶4(K2Fe8O13),K2O∶Fe2O3=1∶5(K2Fe10O16)和/或K2O∶Fe2O3=1∶11(K2Fe22O34)为主活性相,催化剂具有高的机械强度、化学稳定性和长的使用寿命,其活性和选择性也相应有所提高。德国专利DE3821431报导了通过900℃焙烧得到的以K2Fe22O34为主活性相的催化剂,该催化剂的制备选用了专门的氧化铁和任一种含钾的化合物,通过混合-焙烧-水洗-过滤将其制备成直径为0.5-5μm的薄层状制品。中国专利CN1323767A报导了基本组成为Fe-K-Ce-Mo-Mg的催化剂体系,该催化剂以KFeO2为主晶相,使催化剂的活性、再生性能得到提高,延长了使用寿命。中国专利CN1207330A报道了用KOH溶液浸渍氧化铁糊进行煅烧,预先形成KFe11O17的方法。中国专利CN1765753A报道了采用干粉混合法预先形成高铁酸钾KFe11O17的方法,同时控制晶粒大小。中国专利CN1765495A报道了采用在氧化铈、氧化钼中加入高铁酸钾KFe11O17和氧化钙或氧化镁组份的技术,较好地解决了催化剂组成中引入高铁酸钾KFe11O17后催化剂性能变化的问题。
但上述现有技术所公开的脱氢催化剂,其活性和稳定性还需要提高,并需要进一步延长催化剂的使用寿命。
发明内容
本发明提供一种高铁酸钾K2Fe10O16(高杂化度的晶相)和K2Fe22O34(正六方结构的晶相)组合为主活性相的用于乙苯脱氢制备苯乙烯的氧化物催化剂,该催化剂具有较好的活性、稳定性和较长的使用寿命,可适合长周期运行。本发明还公开了该催化剂的制备方法。
为解决上述技术问题,本发明公开了一种乙苯脱氢制苯乙烯的催化剂,以催化剂质量为100份计,包括如下组份:
a)45~75份K2Fe10O16;
b)20~50份K2Fe22O34;
c)1~12份的铈氧化物,以Ce2O3计;
d)1~10份的钼和/或钨氧化物,以MoO3和/或WO3计;
e)1~10份的钙和/或镁氧化物,以CaO和/或MgO计;
其中K2Fe10O16与K2Fe22O34的质量含量比例为1.0~3.5∶1,优选2.0~3.0∶1。
本发明所述的催化剂,高铁酸钾以K2Fe10O16和K2Fe22O34的形式加入,且K2Fe10O16和K2Fe22O34的粒径为0.1~10μm,优选0.5~5μm。
本发明所述的催化剂,铈以氧化物或盐的形式加入,Ce2O3的含量1~12份,优选5~12份;钨和/或钼以氧化物或盐的形式加入,WO3和/或MoO3的含量1~10份,优选1~7份;钙和/或镁以氧化物或盐的形式加入,CaO和/或MgO的含量1~10份,优选1~5份。
本发明所述的催化剂也可以含有助剂V2O5、MnO2、SnO2、Co2O3、La2O3、TiO2、ZrO2、HfO2中的一种或多种,其加入量为本领域技术人员所公知,在CN200810226624.X文献中就介绍了这类助剂的作用和加入量,本发明推荐的加入量为0.001~0.5份。另外,催化剂中还可含有其它常用功能助剂,如1~10份的增强剂水泥和/或1~10份的致孔剂羧甲基纤维素钠。
本发明所述的催化剂中主活性相高铁酸钾主要以K2Fe10O16和K2Fe22O34复配的形式加入,其中K2Fe10O16和K2Fe22O34的质量比例满足1.0~3.5∶1,当K2Fe10O16和K2Fe22O34的质量比例过低时,K2O的利用率低,催化剂活性表现不稳定,使用寿命也偏短;若比例过高,催化剂生产加工成本明显加大,但对催化剂性能作用又相对不大。本发明所述的催化剂,在Ce-Mo(或W)-Ca(或Mg)基本组成的基础上,引入高铁酸钾,高铁酸钾以K2Fe10O16和K2Fe22O34复配的形式加入,使得催化剂Fe-K配比合适,防止了脱氢反应过程中催化剂组分K2O的迁移和流失,从而使得催化剂表现出良好的活性和选择性,又可大大降低催化剂的失活速率,提高其稳定性和使用寿命。
本发明还公开了催化剂的制备方法:将催化剂各个组份先干法混合1-5小时,加入去离子水捏合1-5小时,成型后,经干燥、活化、煅烧10-24小时即可获得催化剂成品。催化剂的干燥、活化条件采用通用的方法,本发明并不特别限定,例如在60-150℃干燥,200-1000℃活化;同样本发明也不特别限定催化剂的形状,推荐催化剂最好为挤条切粒成型,如可以是Φ(2.8-3.3)mm×(5-7)mm的圆柱状催化剂。
本发明公开的制备方法中,所用高铁酸钾K2Fe10O16在催化剂制备前预生成,预生成方法如下:将Fe2O3和K2CO3按照K2Fe10O16的化学计量比混合均匀后,100℃干燥2小时,然后在900-1200℃下焙烧2-6小时,最后通过气流粉碎、球磨等方法即可获得粒径在10μm以下的高铁酸钾K2Fe10O16。
高铁酸钾K2Fe22O34亦为人所知,K2Fe22O34和KFe11O17是一种物质,例如在CN1765495A中揭示一种在组成中引入高铁酸钾K2Fe22O34的乙苯脱氢制备苯乙烯催化剂,其中高铁酸钾K2Fe22O34在催化剂制备前预生成:将Fe2O3和K2CO3以计算量的比例混合均匀后,加入脱离子水制备成膏状物,120℃干燥4小时,然后在900℃下焙烧4小时。在CN1765753A也公开了制备高铁酸钾K2Fe22O34的方法:首先将铁的氧化物、氢氧化物或其盐和钾的氧化物、氢氧化物或其盐的粉体均匀混合后,经挤条、成型、干燥和在温度为800-1100℃下焙烧而成。
其它的组分可以采用市售的产品。
本发明中的乙苯脱氢制苯乙烯催化剂,可适用于异丙基苯、对甲基异丙苯脱氢制异丙烯基苯和对甲基异丙烯基苯。
按上述方法制备的催化剂在等温固定床反应器中进行催化剂的活性评价,评价流程简述如下:
按工艺条件的要求,将乙苯和脱离子水分别经计量泵输入预热混合器,混合汽化后进入反应器,反应器由电热丝外供热,使反应器达到预定温度。其中反应管为不锈钢管,可装填催化剂100mL。脱氢后的产物经急冷器进入冷却器,经气液分离器进行气液分离,液相产物经油水分离器将油和水分离,用气相色谱分析其油相组成。
乙苯转化率和苯乙烯选择性按以下公式计算:
本发明中催化剂的物相组成由XRD测定,测定在德国布鲁克公司D8ADVANCE型X-射线粉末衍射仪上进行,测试条件:管电压40kV,电流40mA,Cu Kα1波长,扫描范围4-70°,扫描速度6°/min,温度25℃。
微米级高铁酸钾K2Fe10O16和K2Fe22O34的晶粒大小经PHILIPS XL-20型扫描电镜(SEM)测定。
催速老化实验是判断催化剂稳定性能的快捷手段。它是指在极端反应条件下使催化剂在短时间内迅速失活,失活速率越慢,表明催化剂稳定性越好。本发明中催速老化条件为:反应温度640℃,水比(重量)1.50,液体空速6.0h-1。催化剂催速老化试验数据见表3。
附图说明
图1本发明实施例5的脱氢催化剂的XRD谱图。图中横坐标为衍射角2θ,纵坐标为衍射强度;
图1中符号说明:
●CeO2-立方晶型-晶胞参数:
a 5.41100-b 5.41100-c 5.41100-α90.000-β90.000-γ90.000;
■K2Fe10O16-六方晶型-晶胞参数:
a 5.93100-b 5.93100-c 35.94000-α90.000-β90.000-γ120.000;
a 5.93000-b 5.93000-c 23.84799-α90.000-β90.000-γ120.000;
由图1可以看出,2θ为31.5°和32.5°的衍射峰分别说明有高铁酸钾K2Fe22O34和K2Fe10O16的存在。
图2本发明实施例5的脱氢催化剂的SEM照片,其中微米级高铁酸钾K2Fe10O16和K2Fe22O34的晶粒大小经XL-20型扫描电镜测定为0.5~5.0微米。
具体实施方式
为了说明本发明的效果,通过实施例和对比例对本发明作进一步的阐述,但本发明并不仅限于这些实施例。
原料来源
本发明的脱氢催化剂在制备过程中所采用的原料厂家分别为:乙苯,兰州石化公司合成橡胶厂产品;氧化铁,石家庄腾龙氧化铁颜料厂产品;氧化钾,沈阳市金诺化工有限公司产品;氧化铈,威海佰德信新材料有限公司产品;氧化钼,天津市同鑫化工厂产品;氧化钨,昆山兴邦钨钼科技有限公司产品。以上原料均为工业级产品。氧化镁,化学纯,上海敦煌化工厂产品;氧化钙,分析纯,上海市奉贤奉城试剂厂产品。其它原料均为市售品。
实施例1
K2Fe22O34的制备:将93.3克氧化铁红和7.2克碳酸钾在捏合机中干混1小时,混合均匀后,加入脱离子水,制成膏状物,120℃干燥4小时,然后置于马福炉中,在900℃下焙烧4小时,即可获得高铁酸钾K2Fe22O34。
K2Fe10O16的制备:将302.1克氧化铁红和51.2克碳酸钾在捏合机中干混1小时,混合均匀后,100℃干燥2小时,然后在1120℃下焙烧3小时,即可获得高铁酸钾K2Fe10O16。
将331.0克K2Fe10O16、95.4克K2Fe22O34、20.1克钨酸铵、16.4克氧化钙,再加25.0克羧甲基纤维素在捏合机中干混2小时后,将105.4克硝酸铈用去离子水溶解后加入捏合机中,捏合2小时,使物料捏合成可挤压的膏状物后取出,经挤条成型、断条工序,制成Φ(2.8~3.3)mm×(5~7)mm的圆柱状催化剂,在80℃下干燥4小时,置于马福炉中分别于300℃下煅烧1小时、560℃下煅烧6小时、780℃下煅烧4小时后,自然降温,即制得成品催化剂进行活性评价,其测试结果见表2。
实施例2
实施例2中高铁酸钾和催化剂的制备方法同实施例1,所不同的是K2Fe10O16275.9克、K2Fe22O34136.6克、钼酸铵19.6克、氧化钙12.5克、氧化镁10克,五氧化二钒0.1克,二氧化锆0.05克,二氧化铪0.05克,硝酸铈128.7克(水溶后加入)、硝酸钴0.1克(水溶后加入)、硝酸镧0.05克(水溶后加入),在120℃下干燥3小时,置于马福炉中分别于340℃下煅烧1小时、600℃下煅烧4小时、850℃下煅烧2小时后,自然降温,即制得成品催化剂进行活性评价,其测试结果见表2。
实施例3
实施例3中高铁酸钾和催化剂的制备方法同实施例1,所不同的是K2Fe10O16339.2克、K2Fe22O34112.3克、钼酸铵8.8克、氧化钙9.5克,二氧化锰0.05克,二氧化锡0.05克,二氧化钛0.1克,再加羧甲基纤维素11.0克、水泥18.0克,硝酸铈83.7克(水溶后加入),对所制得的成品催化剂进行活性评价,其测试结果见表2。
实施例4
实施例4中高铁酸钾和催化剂的制备方法同实施例1,所不同的是K2Fe10O16232.6克、K2Fe22O34191.3克、碳酸钙8.9克、钼酸铵25.6克,在捏合机中干混3小时,将132.9克硝酸铈用去离子水溶解后加入捏合机,对所制得的成品催化剂进行活性评价,其测试结果见表2。
实施例5
将118.0克氧化铁红和9.1克碳酸钾在捏合机中干混1小时,混合均匀后,加入脱离子水,制成膏状物,120℃干燥4小时,然后置于马福炉中,在860℃下焙烧4小时,所得焙烧物在室温下通过气流粉碎即可获得3微米的高铁酸钾K2Fe22O34。
将274.3克氧化铁红和46.5克碳酸钾在捏合机中干混1小时,混合均匀后,100℃干燥2小时,然后在980℃下焙烧5小时,所得焙烧物在室温下通过气流粉碎即可获得3微米的高铁酸钾K2Fe10O16。
实施例5的催化剂制备方法同实施例1,所不同的是3微米的K2Fe10O16300.6克、3微米的K2Fe22O34121.4克、钨酸铵18.1克、碳酸镁11.0克、氧化钙10.9克,再加羧甲基纤维素10.0克、水泥10.0克,硝酸铈122.6克(水溶后加入),对所制得的成品催化剂进行活性评价,其测试结果见表2。
实施例6
实施例6中高铁酸钾和催化剂的制备方法同实施例1,所不同的是K2Fe10O16315.3克、K2Fe22O34110.6克、钼酸铵9.2克、钨酸铵8.7克、氧化钙7.5克、氧化镁5.0克、硝酸铈123.1克(水溶后加入),物料在捏合机中干混2.5小时,加水溶解后捏合1.5小时,经挤条、断条后的圆柱状催化剂在100℃下干燥4小时,置于马福炉中分别于580℃下煅烧4小时、820℃下煅烧4小时后,自然降温,即制得成品催化剂进行活性评价,其测试结果见表2。
表1实施例中各组份的百分含量列表
组成,% | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
K2Fe10O16 | 66.20 | 55.18 | 67.84 | 46.52 | 60.12 | 63.06 |
K2Fe22O34 | 19.08 | 27.32 | 22.46 | 38.26 | 24.28 | 22.12 |
Ce2O3 | 7.97 | 9.73 | 6.33 | 10.05 | 9.26 | 9.31 |
WO3 | 3.46 | - | - | - | 3.11 | 1.50 |
MoO3 | - | 3.20 | 1.43 | 4.17 | - | 1.50 |
CaO | 3.28 | 2.50 | 1.90 | 1.00 | 2.18 | 1.50 |
MgO | - | 2.00 | - | - | 1.05 | 1.00 |
V2O5 | - | 0.02 | - | - | - | - |
MnO2 | - | - | 0.01 | - | - | - |
SnO2 | - | - | 0.01 | - | - | - |
Co2O3 | - | 0.02 | - | - | - | - |
La2O3 | - | 0.01 | - | - | - | - |
TiO2 | - | - | 0.02 | - | - | - |
ZrO2 | - | 0.01 | - | - | - | - |
HfO2 | - | 0.01 | - | - | - | - |
比较例1
按照实施例3的方法制备高铁酸钾和催化剂,所不同的是高铁酸钾仅加入K2Fe22O34451.5克,评价方式同实施例3,评价结果见表2。
比较例2
将900克长约0.4μm,长宽比约5的针状α-Fe2O3边搅拌边加入至悬浮液中,该悬浮液是通过加入200克碳酸钾、200克含水的碳酸铈(分子式以Ce2(CO3)3·xH2O表示,其中铈含量占总重量的40%)、40克的碳酸钙、40克的氧化钨和60克的碱式碳酸镁(分子式以4MgCO3-·Mg(OH)2·4H2O表示,相当于50g MgCO3)到2000mL水中所得。然后对悬浮液进行喷雾干燥,所制得的粉末与120mL水混合30min后转化成膏状物,经挤条切粒成型为Φ3mm×1cm的圆柱状固体,100℃干燥3h,并置于马福炉中,300℃焙烧2h,再经760℃焙烧,即可获得催化剂成品。催化剂的评价方式同实施例3,评价结果见表2。
表2实施例、比较例催化剂性能对比
例子 | 乙苯转化率(%) | 苯乙烯选择性(%) | 苯乙烯收率(%) |
实施例1 | 79.84 | 95.53 | 76.27 |
实施例2 | 80.55 | 95.16 | 76.65 |
实施例3 | 80.16 | 95.51 | 76.56 |
实施例4 | 79.73 | 95.45 | 76.10 |
实施例5 | 80.69 | 95.17 | 76.79 |
实施例6 | 80.32 | 95.49 | 76.70 |
比较例1 | 79.15 | 95.82 | 75.84 |
比较例2 | 77.98 | 95.01 | 74.09 |
评价条件:反应温度为620℃,液体空速为1.0h-1,水油重量比为2.0,催化剂装填量为100mL,常压等温。
表3实施例5中催化剂催速老化实验数据
评价条件:反应温度为640℃,液体空速为6.0h-1,水油重量比为1.5,催化剂装填量为100mL,常压等温。
Claims (14)
1.一种乙苯脱氢制备苯乙烯的催化剂,其特征在于以催化剂质量为100份计,包括如下组份:
a)45~75份K2Fe10O16;
b)20~50份K2Fe22O34;
c)1~12份的铈氧化物,以Ce2O3计;
d)1~10份的钼和/或钨氧化物,以MoO3和/或WO3计;
e)1~10份的钙和/或镁氧化物,以CaO和/或MgO计;
其中K2Fe10O16与K2Fe22O34的质量比例为1.0~3.5∶1。
2.根据权利要求1所述的催化剂,其特征在于K2Fe10O16与K2Fe22O34的质量比例为2.0~3.0∶1。
3.根据权利要求1或2所述的任一催化剂,其特征在于K2Fe10O16和K2Fe22O34的粒径为0.1~10μm。
4.根据权利要求3所述的催化剂,其特征在于K2Fe10O16和K2Fe22O34的粒径为0.5~5μm。
5.根据权利要求1或2所述的催化剂,其特征在于Ce2O35~12份。
6.根据权利要求1或2所述的催化剂,其特征在于WO3和/或MoO31~7份。
7.根据权利要求1或2所述的催化剂,其特征在于CaO和/或MgO 1~5份。
8.根据权利要求1所述的催化剂,其特征在于催化剂含有助剂V2O5、MnO2、SnO2、Co2O3、La2O3、TiO2、ZrO2、HfO2中的一种或多种,加入量为0.001~0.5份。
9.根据权利要求1所述的催化剂,其特征在于催化剂含有1~10份的增强剂和/或1~10份的致孔剂。
10.根据权利要求9所述的催化剂,其特征在于增强剂为水泥,致孔剂为羧甲基纤维素钠。
11.一种权利要求1所述的催化剂的制备方法,其特征在于将催化剂各个组份先干法混合1~5小时,加入去离子水捏合1~5小时,成型后,经干燥、活化、煅烧10~24小时即可获得催化剂成品。
12.根据权利要求11所述的制备方法,其特征在于催化剂在60-150℃干燥,200-1000℃活化。
13.根据权利要求11所述的催化剂,其特征在于铈以氧化物或盐的形式加入;钨和/或钼以氧化物或盐的形式加入;钙和/或镁以氧化物或盐的形式加入。
14.根据权利要求11所述的制备方法,其特征在于K2Fe10O16在催化剂制备前预生成,预生成方法为:将Fe2O3和K2CO3按照K2Fe10O16的化学计量比混合均匀后,100℃干燥2小时,然后在900~1200℃下焙烧2~6小时,最后通过气流粉碎或球磨可获得粒径在10μm以下的高铁酸钾K2Fe10O16。
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