CN1302690A - 丙烯、异丁烯氨氧化流化床催化剂 - Google Patents

丙烯、异丁烯氨氧化流化床催化剂 Download PDF

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CN1302690A
CN1302690A CN99119906A CN99119906A CN1302690A CN 1302690 A CN1302690 A CN 1302690A CN 99119906 A CN99119906 A CN 99119906A CN 99119906 A CN99119906 A CN 99119906A CN 1302690 A CN1302690 A CN 1302690A
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姜家乐
杨斌
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Abstract

本发明属于一种用于丙烯、异丁烯氨氧化制取丙烯腈、甲基丙烯腈的的流化床催化剂,含有的活性组份由通式Mo(12－g)BiaFebNicXdYeZfQgOx表示,其中X为Mg、Co、Ca、Be、Cu、Zn、Pb、Sb、Mn、Cr中的一种或两种以上的混合物;Y为La、Ce、Sm中的一种或两种以上的混合物;Z为K、Rb、Na、Cs中的一种或两种以上的混合物;Q为B、W、P、V中的一种或两种以上的混合物;a~f为相应元素的原子数,x为满足其它元素化合价所需的氧原子总数。与已有技术相比,本催化剂可以较低的氧比和氨比以及较低的温度进行反应,且有较高的丙烯腈收率。

Description

丙烯、异丁烯氨氧化流化床催化剂
本发明涉及由烯烃氨氧化制取不饱和腈的催化剂，其活性组份含有钼、铋、铁等多种金属氧化物。
Mo-Bi催化剂是用于烯烃制取不饱和腈(如由丙烯、异丁烯氨氧化制取丙烯腈或甲基丙烯腈)的反应中较成熟和较常用的催化剂，且自诞生以来不断有专利推出新的改进配方。如在活性组份中加入过渡金属以提高活性，增加产物的单收；加入稀土元素改善氧化还原能力；加入Na、P等元素以提高催化剂的耐磨性；加入Fe、Co、Ni等元素以抑制Mo的挥发，提高催化剂的稳定性等等。而近年来对丙烯腈催化剂的研究已较多地注重催化剂能够高效地利用氧或氨，即可以较低的氧比和氨比进行反应。显然，较低的氧比和氨比使得收率提高，然而低氨比具有更重要的意义是降低了反应尾气中未反应氨的含量，从而可相应减少用于中和未反应氨的酸的用量，这对降低生产成本和环境污染的控制都是极为有利的。专利CN 96101529.2介绍了一种改进的Mo-Bi催化剂，其优点是催化剂具有较好的氧化还原稳定性、反应可以较低的氧比和氨比进料而仍有较好的反应收率。
本发明的目的是提供一种新的Mo-Bi催化剂，与上述对比文献介绍的同类催化剂相比，除仍具备其拥有的优点外，同时还有相对更高的丙烯转化率和较高的丙烯腈或甲基丙烯腈单程收率。
本发明提供的Mo-Bi催化剂含有Mo、Bi、Fe、Ni，以及任选地含有Mg、Co、Ca、Be、Cu、Zn、Pb、Sb、Mn、Cr、La、Ce、Sm、K、Rb、Na、Cs、B、W、P或V中的一种或多种金属氧化物，其含有的活性组份由下列通式表示：
           Mo(12-g)BiaFebNicXdYeZfQgOx
其中：
X为Mg、Co、Ca、Be、Cu、Zn、Pb、Sb、Mn、Cr中的一种或两种以上的混合物，
Y为La、Ce、Sm中的一种或两种以上的混合物，
Z为K、Rb、Na、Cs中的一种或两种以上的混合物，
Q为B、W、P、V中的一种或两种以上的混合物，
a=0.1～6，b、c、d、e、g=0.1～10，f=＞0～0.5，x为满足其它元素化合价所需的氧原子总数。
催化剂所用的载体为二氧化硅或氧化铝或两者的混合物，其含量为催化剂总量的(40～60)％(w.t.)。
然而，X最好为Mg或Co或其混合物；Y最好为La或Ce或其混合物；Z最好为Rb或Cs或其混合物；Q最好为W或V或其混合物。载体最好选用二氧化硅。
催化剂可用本领域技术人员熟悉的混浆法制备，或用通常熟知的其它方法进行制备，用于制备催化剂各组份的原料一般采用硝酸盐或其它可溶于水的盐类或酸类，以便各组份混合均匀。
与已有技术相比，本发明提供的催化剂具有较好的氧化还原能力，在范围更宽的反应条件下有很好的氧化还原稳定性，从而可以较低的空气/烯烃比以及较低的氨/烯烃而仍能得到较高的产物单收，在保持较高的烯烃转化率的前提下，丙烯腈或甲基丙烯腈的选择性有较显著的提高。另外，本发明提供的催化剂还相对具有更低的反应操作温度，这将有利于提高催化剂的使用寿命。
下面将通过实施例来进一步描述本发明的细节，通过实施例的评价数据可明显地看出本发明的积极效果。
在以下给出的实施例中，对催化剂考察评价的具体条件为：反应器      ：流化床反应器，内径38mm催化剂填装量：550克反应器顶压力：0.085MPa(表压)反应温度    ：420/410℃反应时间    ：4小时原料比(摩尔比)：  丙烯/氨/空气=1/1.15或1.05/9.5WWH         ：0.06
反应产物用0℃酸液和水吸收，用气相色谱和化学分析结合分析产物。并计算碳平衡，当碳平衡在(95～105)％时为有效数据。
丙烯转化率、丙烯腈收率和选择性的定义为：
Figure A9911990600062
实施例1.
将423.2克(NH4)6Mo7O24·4H2O加入到330克70℃的温水中，搅拌使其全部溶解，再加入1250克40％(w.t.)的硅溶胶，制成物料A。
将166克Fe(NO3)3·9H2O加入40克的70℃热水中，搅拌溶解后再加入91.3克Bi(NO3)3·5H2O,292.8克Ni(NO3)3·6H2O,104.5克Mg(NO3)3·6H2O,46.7g Sm(NO3)3·nH2O,搅拌溶解后制成物料B。
在20克水中加入1.9克KNO3和1.5克RbNO3，溶解后将其加入物料B中形成物料C。
将物料C在快速搅拌下滴加于物料A中，于70℃老化3小时后喷雾干燥，将所得的颗粒在回转焙烧炉中于580℃下焙烧3小时，得成品催化剂。实施例2～13
催化剂的制备方法同实施例1，仅采用相应不同的起始物料及其用量。
实施例1～13制备催化剂的起始物料及相应的用量列于表1，各催化剂活性组份的组成见表2。
成品催化剂按上述考察评价条件进行考察，其结果见表3。
表1．(单位：克)
(NH4)6MO7O24· 4H2O  Bi(NO3)3·5H2O  Fe(NO3)3·9H2O  Ni(NO3)2·6H2O  Mg(NO3)2·6H2O  Ce(NO3)3·6H2O  La(NO3)3·nH2O  Sm(NO3)3·nH2O Sb2O3 CrO3 Mn(NO3)2 Pb(NO3)2 KNO3 RbNO3 CsNO3 NaNO3  H7P(W2O7)·nH2O NH4VO3
实施例1  423.2  101.4  149.4  405.6  104.5  -  44.4  -  -  -  --  -  1.9  2．4  -  -  -  4.7
实施例2  419.4  50.7  124.5  292.2  125.4  26.6  -  -  41.4  --  -  -  1.7  -  0.4  0.9  14.7  -
实施例3  408.7  20.3  199.2  268.4  94.1  53.2  -  -  69.0  --  -  -  0.4  2.1  2.4  -  4.9  11.8
实施例4  405.3  20.3  132.8  280.3  104.5  -  17.8  -  117.3  10.2  -  -  1.1  0.6  1.6  -  -  16.5
实施例5  394.5  101.4  157.7  149.1  62.7  71.0  -  -  138.0  --  -  -  0.4  2.4  2.0  -  39.2  4.7
实施例6  398.1  405.6  207.5  238.6  104.5  -  44.4  -  117.3  -  14.5  -  0.8  -  2.0  0.4  19.6  11.8
实施例7  416.1  456.3  149.4  369.8  104.5  26.6  35.5  -  72.5  4.1  -  -  1.7  1.5  -  0.8  -  9.4
实施例8  405.3  50.7  265.6  345.9  167.2  -  44.4  -  96.6  4.1  3.6  -  -  2.4  2.0  -  14.7  9.4
实施例9  412.5  243.4  207.5  310.1  104.5  -  -  -  117.3  --  7.3  121.0  -  2.7  2.4  -  -  11.8
实施例10  401.7  111.5  149.4  405.6  73.2  -  -  -  96.6  10.2  -  235.2  0.8  2.7  -  -  39.2  -
实施例11  412.5  182.5  199.2  268.4  94.1  -  -  -  -  --  -  302.4  1.5  1.5  -  0.4  14.7  4.7
实施例12  394.5  142.0  149.4  238.6  146.3  -  -  -  55.2  20.3  36.3  134.4  -  4.5  -  1.2  9.8  18.8
实施例13  365.8  354.9  166.0  381.7  94.1  17.7  71.0  -  138.0  --  7.3  241.9  -  0.6  3.2  -  49.0  18.8
表2.实施例1.    K0.09Mo11.8Bi1Fe1.8Ni6.8Mg2La0.5Rb0.05V0.2实施例2.    K0.08Mo11.7Bi0.5Fe1.5Ni4.9Mg2.4Sb1.2Ce0.3Na0.05Cs0.01W0.3实施例3.    K0.02Mo11.4Bi0.2Fe2.4Ni4.5Mg1.8Sb2Ce0.6Rb0.07Cs0.06V0.5W0.1实施例4.    K0.05Mo11.3Bi0.2Fe1.6Ni4.7Mg2Sb3.4Cr0.5La0.2Rb0.02Cs0.04V0.7实施例5.    K0.02Mo11Bi1Fe1.9Ni2.5Mg1.2Sb4.0Ce0.8Rb0.08Cs0.05V0.2W0.8实施例6.    K0.04Mo11.1Bi4.0Fe2.5Ni4.0Mg2Sb3.4La0.5Mn0.4Cs0.05Na0.02V0.5W0.4实施例7.    K0.08Mo11.6Bi4.5Fe1.8Ni6.2Mg2Sb2.1Ce0.3La0.4Cr0.2Rb0.05Na0.04V0.4实施例8.    Mo11.3Bi0.5Fe3.2Ni5.8Mg3.2Sb2.8La0.5Cr0.2Mn0.1Rb0.08Cs0.05V0.4W0.3实施例9.    Mo11.5Bi2.4Fe2.5Ni5.2Mg2Sb3.4Pb1.8Mn0.2Rb0.09Cs0.06V0.5实施例10.   K0.04Mo11.2Bi1.1Fe1.8Ni6.8Mg1.4Sb2.8Pb3.5Cr0.5Rb0.09W0.8实施例11.   K0.07Mo11.5Bi1.8Fe2.4Ni4.5Mg1.8Cu2Pb4.5Rb0.05Na0.02V0.2W0.3实施例12.   Mo11Bi1.4Fe1.8Ni4.0Mg2.8Sb1.6Pb2Mn1Cr1Rb0.15Na0.06V0.8W0.2实施例13    Mo10.2Bi3.5Fe2Ni6.4Mg1.8Sb4Pb3.6Ce0.2La0.8Mn0.2Rb0.2Cs0.08V0.8W1注：上述催化剂的载体SiO2为50％(w.t.)表3.
    丙烯腈单收  丙烯转化率  丙烯腈选择性  反应温度  氨/丙烯
       (％)        (％)       (％)          (℃)实施例1    84.31      98.81       85.33         420      1.15
       83.75      99.42       84.24         410      1.05实施例2    83.68      98.78       84.71         420      1.15实施例3    80.43      98.84       81.37         420      1.15实施例4    83.57      98.48       84.86         420      1.15实施例5    84.72      98.93       85.64         420      1.15
       84.04      99.66       84.33         410      1.05实施例6    84.80      98.97       85.68         420      1.15
       83.68      99.71       83.92         410      1.05实施例7    81.78      98.42       83.09         420      1.15实施例8    84.95      98.78       86.00         420      1.15
       84.15      99.59       84.50         410      1.05实施例9    83.45      98.82       84.45         420      1.15实施例10   84.82      98.96       85.71         420      1.15
       83.96      99.82       84.11         410      1.05实施例11   82.74      98.81       83.74         420      1.15实施例12   84.59      98.74       85.67         420      1.15
       83.41      99.58       83.67         410      1.05实施例13   85.18      98.86       86.16         420      1.15
       84.78      99.46       85.24         410      1.05

Claims (6)

1、一种用于丙烯、异丁烯氨氧化制取丙烯腈、甲基丙烯腈的流化床催化剂，含有Mo、Bi、Fe、Ni，以及任选地含有Mg、Co、Ca、Be、Cu、Zn、Pb、Sb、Mn、Cr、La、Ce、Sm、K、Rb、Na、Cs、B、W、P或V中的一种或多种金属氧化物，其含有的活性组份由下列通式表示：
                  Mo(12-g)BiaFebNicXdYeZfQgOx
其中：
x为Mg、Co、Ca、Be、Cu、Zn、Pb、Sb、Mn、Cr中的一种或两种以上的混合物，
Y为La、Ce、Sm中的一种或两种以上的混合物，
Z为K、Rb、Na、Cs中的一种或两种以上的混合物，
Q为B、W、P、V中的一种或两种以上的混合物，
a=0.1～6,b、c、d、e、g=0.1～10,f=＞0～0.5,x为满足其它元素化合价所需的氧原子总数。
催化剂所用的载体为二氧化硅或氧化铝或两者的混合物，其含量为催化剂总量的(40～60)％(w.t.)。
2、根据权利要求1所述的催化剂，其特征在于X为Mg或Co或其混合物。
3、根据权利要求1所述的催化剂，其特征在于Y为La或Ce或其混合物。
4、根据权利要求1所述的催化剂，其特征在于Z为Rb或Cs或其混合物。
5、根据权利要求1所述的催化剂，其特征在于Q为W或V或其混合物。
6、根据权利要求1、2、3或4所述的催化剂，其特征在于所用的载体为二氧化硅。
CN99119906A 1999-10-28 1999-10-28 丙烯、异丁烯氨氧化流化床催化剂 Expired - Lifetime CN1104282C (zh)

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US7071140B2 (en) 2002-12-02 2006-07-04 The Standard Oil Company Catalyst for the manufacture of acrylonitrile
US7348291B2 (en) 2002-12-02 2008-03-25 Ineos Usa Llc Catalyst for the manufacture of acrylonitrile
CN100398204C (zh) * 2005-08-15 2008-07-02 中国石油化工股份有限公司 丙烯氨氧化生产丙烯腈催化剂
US8258073B2 (en) 2010-03-23 2012-09-04 Ineos Usa Llc Process for preparing improved mixed metal oxide ammoxidation catalysts
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US8420566B2 (en) 2010-03-23 2013-04-16 Ineos Usa Llc High efficiency ammoxidation process and mixed metal oxide catalysts
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CN107073456A (zh) * 2014-05-29 2017-08-18 英尼奥斯欧洲股份公司 改进的选择性氨氧化催化剂
CN112121811A (zh) * 2019-11-15 2020-12-25 北京水木滨华科技有限公司 一种制备甲基丙烯腈用催化剂及制备甲基丙烯腈的方法

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* Cited by examiner, † Cited by third party
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US7071140B2 (en) 2002-12-02 2006-07-04 The Standard Oil Company Catalyst for the manufacture of acrylonitrile
US7348291B2 (en) 2002-12-02 2008-03-25 Ineos Usa Llc Catalyst for the manufacture of acrylonitrile
CN100398204C (zh) * 2005-08-15 2008-07-02 中国石油化工股份有限公司 丙烯氨氧化生产丙烯腈催化剂
US8258073B2 (en) 2010-03-23 2012-09-04 Ineos Usa Llc Process for preparing improved mixed metal oxide ammoxidation catalysts
US8350075B2 (en) 2010-03-23 2013-01-08 Ineos Usa Llc Mixed metal oxide ammoxidation catalysts
US8420566B2 (en) 2010-03-23 2013-04-16 Ineos Usa Llc High efficiency ammoxidation process and mixed metal oxide catalysts
US8455388B2 (en) 2010-03-23 2013-06-04 Ineos Usa Llc Attrition resistant mixed metal oxide ammoxidation catalysts
CN107073456A (zh) * 2014-05-29 2017-08-18 英尼奥斯欧洲股份公司 改进的选择性氨氧化催化剂
CN112121811A (zh) * 2019-11-15 2020-12-25 北京水木滨华科技有限公司 一种制备甲基丙烯腈用催化剂及制备甲基丙烯腈的方法

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