CN1054914A - 丙烯腈流化床催化剂 - Google Patents
丙烯腈流化床催化剂 Download PDFInfo
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Abstract
本发明是一种用于丙烯氨氧化法制造丙烯腈的
流化床催化剂,是由二氧化硅载体和化学式如下的组
合物组成:
AaBbCcNidCoeNafFegBihMiMojOx
式中A为钾、铷、铯、钐、铊或它们的混合物;B
为锰、镁、锶、钙、钡、镧、稀土元素或它们的混合物;C
为磷、砷、硼、锑、铬或它们的混合物;M为钨、钒或它
们的混合物。本发明催化剂除了对生成丙烯腈有很
高的活性和选择性外,更重要的是适用于空气与丙烯
在低配比条件下进行催化反应,从而使反应器生产能
力大幅度增加。采用本发明催化剂,反应器的生产能
力比目前常用的催化剂提高10-15%。
Description
本发明是一种用于丙烯氨氧化生成丙烯腈的流化床催化剂,由二氧化硅载体和化学式如下的组合物组成:
式中A为钾、铷、铯、钐、铊或它们的混合物;B为锰、镁、锶、钙、钡、镧、稀土元素或它们的混合物;C为磷、砷、硼、锑、铬或它们的混合物;M为钨、钒或它们的混合物。
a为0.01-1、最佳为0.03-0.4,b为0.1-3、最佳为0.5-2,c为0.01-2、最佳为0.1-1.5,d为0.01-8、最佳为0.5-5,e为0.01-12、最佳为0.5-8,f为0.2-0.7、最佳为0.3-0.5,g为0.01-8、最佳为0.1-4,h为0.01-6、最佳为0.1-4,i为0.01-6、最佳为0.1-3,j为6-11.99、最佳为9-11.99。式中i与j的和恒为12,x为满足催化剂中各元素化合价所需氧原子数的总和。
催化剂中载体二氧化硅含量为30-70%(重量),最佳为40-60%(重量)。
中国专利87103455.7(CN1005248B)已经指明由钠元素和其它元素的氧化物组成的催化剂具有高活性和优良的耐磨性。发明人在中国专利87103455.7(CN1005248B)的基础上进一步研究得出,如果用钨和钒代替部分钼组分时,除了能提高催化剂的活性和选择性外,更重要的是能显著降低反应器进料中的空气与丙烯的配比,而使反应器的生产能力明显增加,与中国专利87103455.7(CN1005248B)所述的催化剂相比较,产量可增加10-15%。
本发明催化剂化学式中的A类元素为钾、铷、铯、钐、铊,它们对改善催化剂的活性有明显作用,这在中国专利87103455.7(CN1005248B),美国专利4162234,日本专利特公昭58-2232均有说明,但这些专利所用的A类元素一般为一种,最多同时使用二种;而本发明的催化剂化学式中的A类元素是三种或三种以上的组合。本发明的催化剂中的A类元素可任意组合,但以钾、铷和铯;铯、钐和铊;铷、铯和钐及钾、铯和铊的几种组合形式较好。催化剂中三种A类元素在AaBbCcNidCoeNafFegBihMiMojOx的化学式中的a的总和值范围为0.01-1,最佳为0.03-0.4。
用钨组分代替部分钼组分对提高催化剂对丙烯腈的选择性在日本专利特公昭50-38084、日本专利特开昭49-10818、中国专利CN-86101301A中已有报道。所报道的催化剂除了化学组分与本发明的催化剂有所不同外,活性数据多数是在固定床反应器取得的,从少数流化床反应器考察数据来看,也低于本发明的结果。在本发明的催化剂中钨和钒组分的加入量有一定范围,i值为0.01-6。当M是钨时,最佳为0.1-3;当M是钒时,i值最佳为0.1-3。M加入量少对催化剂的性能的改进无效果,过多则使催化剂活性下降。
本发明的要点就是在原有的催化剂(中国专利87103455.7,CN1005248B)中加入多种A类元素和用钒和钨代替部分钼制成的一种催化剂。
本发明的催化剂制造方法可按常法进行。首先将催化剂各组分与载体和水混合成浆料,经喷雾干燥成型为微球状,最后焙烧制成催化剂。浆料的配制是将催化剂各组分的水溶液和载体按中国专利87103455.7(CN1005248B)所述的方法进行。
本发明催化剂中各组分所使用的原料为:
组分A类元素最好用硝酸盐,氢氧化物或可分解为氧化物的盐类。
组分B类元素可用氧化物或可分解为氧化物的盐类。
组分C类元素中的磷、砷和硼最好用相应的酸类或其铵盐,铬最好用三氧化铬(六价铬)、硝酸铬或二者的混合物,锑可用三氧化二锑、五氧化二锑、水解生成氧化锑的卤化物及锑溶胶。
组分钠可用硝酸钠、氢氧化钠、硅酸钠或任何可以分解的钠化合物。
组分镍、钴、铁、铋可用氧化物或分解为氧化物的盐类,所用的盐类最好是水溶性的硝酸盐。
组分M类元素中的钨可用氧化钨或钨酸铵,钒用偏钒酸铵。
组分钼可用氧化钼或钼酸铵。
作为载体的二氧化硅的原料可用硅溶液,其质量要符合中国专利87103455.7(CN1005248B)的规定。
配制好的浆料经过热处理后进行喷雾成型。喷雾干燥器可用压力式、两流式和离心转盘式,但以离心转盘式较好,能保证制成的催化剂具有良好的粒度分布范围。
催化剂的焙烧分为两个阶段,催化剂中各元素盐类的分解和高温焙烧。其分解阶段温度为200-400℃,时间为0.5-2小时,焙烧温度为500-800℃,最好是550-650℃。分解和焙烧在两个焙烧炉中分别进行,也可以在一个焙烧炉中分两个阶段进行,或者在连续式旋转焙烧炉内将分解和焙烧同时进行。但在催化剂分解和焙烧过程中,需注意焙烧炉内应有适量的空气流通。
采用本发明催化剂制造丙烯腈所需的丙烯、氨和分子氧的规格与使用其他催化剂的相同。虽然原料丙烯中的低分子量饱和烃的含量对反应并无影响,但从经济观点考虑,丙烯浓度应大于85%(摩尔)。氨可用肥料级液氨。反应所需的分子氧从技术观点出发可用纯氧、富氧空气,但从经济、资源方便考虑,用空气作为分子氧源更为合理。
进入流化床反应器的氨与丙烯的摩尔比可在0.8∶1到1.5∶1之间变化,但最佳在1.0∶1到1.3∶1之间变化。空气与丙烯的实际摩尔比最好为8∶1到10∶1之间,这样低的配比是本发明催化剂的重要优点。如果由于某些原因须采用较高的空气比时,可以增大到11∶1,这对反应没有明显不利影响。但从安全角度考虑,反应气体中氧的体积含量不能大于7%,最好不大于4%。
在流化床反应器上采用本发明催化剂时,反应温度在420-490℃,最佳为440-460℃,反应压力一般为0.01-0.2兆帕,最佳为0.04-0.2兆帕。
催化剂的丙烯负荷(WWH)为0.04-0.20,最好为0.05-0.10。
WWH的定义为:
WWH=丙烯进料重量/(催化剂重量×小时)
用本发明催化剂制造丙烯腈的产品回收精制工艺与一般方法相同,即流化床反应器流出气体经中和塔除去未反应氨,再用水在吸收塔中将全部有机物吸收。吸收液经萃取蒸馏,脱除氢氰酸和水得高纯度丙烯腈产品。
以下是本发明催化剂的实施例,其中丙烯转化率、丙烯腈选择性和单程收率的定义如下:
丙烯转化率(%)= (反应的丙烯摩尔数)/(丙烯进料摩尔数) ×100
丙烯腈选择性(%)= (生成丙烯腈摩尔数)/(反应的丙烯摩尔数) ×100
丙烯腈单程收率(%)= (生成丙烯腈摩尔数)/(丙烯进料摩尔数) ×100
[实例1] 将9.2克重量浓度为20%的硝酸钾溶液,13.4克重量浓度为20%的硝酸铷溶液,8.9克重量浓度为20%的硝酸铯溶液和23.2克重量浓度为20%的硝酸钠溶液混合为物料(Ⅰ)。
将23.7克钨酸铵溶于100毫升重量浓度为5%的氨水,再与368.3克钼酸铵与300毫升50-95℃热水组成的溶液相混合得物料(Ⅱ)。
将79.2克硝酸铋、52.1克硝酸锰、131.9克硝酸铁、211.1克硝酸钴、121.3克硝酸镍和29.0克硝酸铬混合,加水70毫升,加热后溶解,得物料(Ⅲ)。
将物料(Ⅰ)与1250克重量浓度为40%的氨稳定无钠硅溶胶混合,在搅拌下加入5.23克重量浓度为85%的磷酸和物料(Ⅱ)和(Ⅲ),充分搅拌得浆料。按常法将制成的浆料在喷雾干燥器中成型为微球状,最后在内径为89毫米、长度为1700毫米(φ89×1700mm)的旋转焙烧炉中于670℃焙烧1小时,制成的催化剂组成为:
Mo11.5W0.5Bi0.9Fe1.8Co4.0Ni2.3Mn1.0Cr0.4P0.25Na0.3K0.1Rb0.1Cs0.05+50%SiO2
制成的催化剂放入内径为38毫米的流化床反应器内,在反应温度为435℃,反应压力为0.08兆帕,丙烯∶氨∶空气=1∶1.2∶9.2(摩尔),WWH为0.045的条件下进行活性评价,结果如下:
丙烯转化率: 96.2%
丙烯腈选择性: 83.3%
丙烯腈单收: 80.1%
此配比下丙烯投料量为245毫升/分,则丙烯腈生成量为:
(245/22.4)×0.801×53=464.3克/分
如果将原料配比改为丙烯∶氨∶空气=1∶1.5∶10.5,其余工艺条件不变的情况下进行活性评价,结果如下:
丙烯转化率: 97.8%
丙烯腈选择性: 81.0%
丙烯腈单收: 79.2%
此配比下丙烯投料量为219毫升/分,则丙烯腈生成量为:
(219/22.4)×0.792×53=410克/分
[实例2] 按实例1所述方法制造催化剂,但物料(Ⅰ)用重量浓度均为20%的15.6克硝酸铷溶液,10.4克硝酸铯溶液,47.4克硝酸钐溶液和27.2克硝酸钠溶液相混的物料。
物料(Ⅱ)是用55.7克钨酸铵溶于300毫升重量浓度为5%的氨水和414.2克钼酸铵与350毫升50-95℃热水组成的溶液相混合而成的物料。
用93.1克硝酸铋,155.1克硝酸铁,61.2克硝酸锰,248.3克硝酸钴,142.6克硝酸镍,34.1克硝酸铬和100毫升水配制而成物料(Ⅲ)。
与实例1的制法相同,将上述物料与1000克重量浓度为40%的硅溶胶和6.15克重量浓度为85%的磷酸混合,成型,焙烧制成的催化剂组成为:
Mo11.0W1.0Bi0.9Fe1.8Co4.0Ni2.3Mn1.0Cr0.4P0.25Rb0.1Cs0.1Sm0.1Na0.3+40%SiO2
催化剂活性的考察方法与实例1相同,但丙烯∶氨∶空气=1∶1.2∶9.4,其余工艺条件不变,活性评价的结果如下:
丙烯转化率: 98.5%
丙烯腈选择性: 83.1%
丙烯腈单收: 81.9%
[实例3] 按实例1所述方法制造催化剂,物料(Ⅰ)用重量浓度均为20%的9.3克硝酸钾溶液,8.9克硝酸铯溶液,24.3克硝酸亚铊溶液和23.3克硝酸钠溶液混合制成。
物料(Ⅱ)是用9.5克钨酸铵溶于50毫升重量浓度为5%的氨水,再和380.1克钼酸铵与300毫升50-95℃热水组成的溶液混合制成。
用79.7克硝酸铋,132.7克硝酸铁,212.4克硝酸钴,122.0克硝酸镍,52.4克硝酸锰,29.2克硝酸铬和70毫升水配制成物料(Ⅲ)。
与实例1的制法相同,将上述各物料与1250克重量浓度为40%的硅溶胶和3.16克重量浓度为85%的磷酸及10毫升水中含有1.13克硼酸溶液混合,成型,焙烧,制成的催化剂组成为:
Mo11.8W0.2Bi0.9Fe1.8Co4.0Ni2.3Mn1.0Cr0.4P0.15B0.1Na0.3K0.1Cs0.05Tl0.1+50%SiO2
催化剂活性的考察方法与实例1相同,但丙烯∶氨∶空气=1∶1∶8.9,其余工艺条件不变,活性评价的结果如下:
丙烯转化率: 96.1%
丙烯腈选择性: 82.9%
丙烯腈单收: 79.7%
[实例4] 按实例1所述方法制造催化剂,但物料(Ⅰ)用重量浓度均为20%的9.0克硝酸铯溶液,41.0克硝酸钐溶液,24.6克硝酸亚铊溶液和23.5克硝酸钠溶液混合制成。
物料(Ⅱ)是用24.1克钨酸铵溶于100毫升重量浓度为5%的氨水溶液中,再和374.1克钼酸铵与300毫升50-95℃热水组成的溶液相混合而成的物料。
用80.4克硝酸铋,134.04克硝酸铁,52.9克硝酸锰,94.5克硝酸镁,107.2克硝酸钴,123.2克硝酸镍,29.5克硝酸铬与70毫升水配制成物料(Ⅲ)。
与实例1的制法相同,将上述各物料与1250克重量浓度为40%的硅溶胶和5.31克重量浓度为85%的磷酸混合,成型,焙烧,制成的催化剂组成为:
Mo11.5W0.5Bi0.9Fe1.8Co2.0Mg2.0Ni2.3Mn1.0Cr0.4P0.25Cs0.05Sm0.1Tl0.1Na0.3+50%SiO2
催化剂活性的考察方法与实例1相同,但丙烯∶氨∶空气=1∶1.15∶9.5,其余工艺条件不变,活性评价的结果如下:
丙烯转化率: 95.5%
丙烯腈选择性: 81.5%
丙烯腈单收: 78.9%
[实例5] 按实例1所述方法制造催化剂,但物料(Ⅰ)用重量浓度均为20%的22.1克硝酸钠溶液,17.5克硝酸钾溶液,8.5克硝酸铯溶液混合制成。
物料(Ⅱ)是用4.05克偏钒酸铵和361.0克钼酸铵与300毫升50-95℃热水混合制成。
用84.1克硝酸铋,140.0克硝酸铁,75.2克硝酸亚铈,242.0克硝酸钴,74.6克硝酸锰,18.7克硝酸铬,11.54克硝酸铊与100毫升水配制成物料(Ⅲ)。
与实例1的制法相同,将上述各物料与1250克重量浓度为40%的硅溶胶和16.1克硼酸混合,成型,焙烧制成的催化剂组成为:
Mo11.8V0.2Bi1Fe2Ce1Co4.8Mn1.5Cr0.27Na0.3K0.2Tl0.25Cs0.05B1.5+50%SiO2
催化剂活性的考察方法与实例1相同,但丙烯∶氨∶空气=1∶1.1∶9.4,其余工艺条件不变,活性评价的结果如下:
丙烯转化率: 97.8%
丙烯腈选择性: 81.5%
丙烯腈单收: 79.7%
[实例6] 按实例1所述方法制造催化剂,但物料(Ⅰ)用重量浓度均为20%的21.6克硝酸钠溶液,8.6克硝酸钾溶液,12.15克硝酸铷溶液,8.3克硝酸铯混合制成。
物料(Ⅱ)是用82.2克硝酸铋,136.9克硝酸铁,110.1克硝酸镧,98.7克硝酸钴,98.6克硝酸镍,73.0克硝酸锰,20.3克硝酸铬与80毫升水混合制成。
由314.3克钼酸铵,66.4克钨酸铵,5.95克偏钒酸铵与300毫升热的(50-95℃)重量浓度为5%的氨水中制成物料(Ⅲ)。
与实例1的制法相同,上述各物料与9.8克重量浓度为85%的磷酸和1250克重量浓度为40%的硅溶胶混合,成型,焙烧,制成的催化剂组成为:
Mo10.5W1.2V0.3Bi1Fe2La1.5Co2Ni2Mn1.5Cr0.3Na0.3K0.1Rb0.1Cs0.05P0.5+50%SiO2
催化剂活性的考察方法与实例1相同,但丙烯∶氨∶空气=1∶1.15∶9.1,其余工艺条件不变,活性评价的结果如下:
丙烯转化率: 94.5%
丙烯腈选择性: 84.1%
丙烯腈单收: 79.5%
Claims (3)
1、一种用于丙烯、氨和分子氧反应生产丙烯腈的流化床催化剂,由二氧化硅载体和化学式如下的组合物组成:
式中A为钾、铷、铯、钐、铊或它们的混合物;B为锰、镁、锶、钙、钡、镧、稀土元素或它们的混合物;C为磷、砷、硼、锑、铬或它们的混合物;M为钨、钒或它们的混合物。
a为0.01-1,b为0.1-3,c为0.01-2,d为0.01-8,e为0.01-12,f为0.2-0.7,g为0.01-8,h为0.01-6,i为0.01-6,j为6-11.99,x为满足催化剂中各元素化合价所需的氧原子总数。其特征在于M可以是钨、钒单用或钨与钒混用。A类元素中钾、铷、铯、钐、铊为三种或三种以上组合而成。化学式中i与j的和恒为12。
催化剂中载体二氧化硅含量为30-70%(重量)。
2、根据权利要求1所述的催化剂,其中a为0.03-0.4,b为0.5-2,c为0.1-1.5,d为0.5-5,e为0.5-8,f为0.3-0.5,g为0.1-4,h为0.1-4,i为0.1-3,j为9-11.99,x为满足催化剂中其它元素化合价所需的氧原子总数。
催化剂中载体二氧化硅含量为40-60%(重量)。
3、根据权利要求1所述的催化剂,其特征在于A类元素的组合为钾、铷和铯;铯、钐和铊;铷、铯和钐及钾、铯和铊。
Priority Applications (4)
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CN90108811A CN1021638C (zh) | 1990-11-05 | 1990-11-05 | 丙烯腈流化床催化剂 |
DE69102245T DE69102245T2 (de) | 1990-11-05 | 1991-10-29 | Fliessbett-Katalysator für die Herstellung von Acrylnitril. |
EP91118387A EP0484792B1 (en) | 1990-11-05 | 1991-10-29 | Fluidized-bed catalyst for preparing acrylonitrile |
US07/786,217 US5223469A (en) | 1990-11-05 | 1991-10-31 | Fluidized-bed catalyst for preparing acrylonitrile |
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CN90108811A CN1021638C (zh) | 1990-11-05 | 1990-11-05 | 丙烯腈流化床催化剂 |
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CN1054914A true CN1054914A (zh) | 1991-10-02 |
CN1021638C CN1021638C (zh) | 1993-07-21 |
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US (1) | US5223469A (zh) |
EP (1) | EP0484792B1 (zh) |
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DE (1) | DE69102245T2 (zh) |
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-
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- 1991-10-29 EP EP91118387A patent/EP0484792B1/en not_active Expired - Lifetime
- 1991-10-29 DE DE69102245T patent/DE69102245T2/de not_active Expired - Fee Related
- 1991-10-31 US US07/786,217 patent/US5223469A/en not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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DE69102245T2 (de) | 1994-10-06 |
EP0484792B1 (en) | 1994-06-01 |
US5223469A (en) | 1993-06-29 |
EP0484792A1 (en) | 1992-05-13 |
DE69102245D1 (de) | 1994-07-07 |
CN1021638C (zh) | 1993-07-21 |
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