CN103524312A - 制备甲基丙烯醛的方法 - Google Patents
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Abstract
本发明涉及一种由异丁烯或叔丁醇氧化制甲基丙烯醛的方法,主要解决现有技术中甲基丙烯醛收率不高和选择性不好的问题。本发明通过采用以选自SiO2或Al2O3中的至少一种为载体并含有由下列通式的活性组分Mo12BiaFebCocCedXeYfZgOx,其中X为选自W、V、Ni、Cr、Mn、Nb或Re中的至少一种;Y为选自Sn、Sr、Zn、Ti或Zr中的至少一种;Z为选自K、Rb、Na、Li、Tl或Cs中的至少一种,在催化剂制备过程中加入有机物作造孔剂的技术方案,较好地解决了该问题,可用于甲基丙烯醛的工业生产中。
Description
技术领域
本发明涉及一种异丁烯或叔丁醇氧化制甲基丙烯醛的方法。
背景技术
甲基丙烯酸甲酯(MMA)是一种重要的有机化工原料和化工产品,主要用于生产聚甲基丙烯酸甲酯(有机玻璃,PMMA)、聚氯乙烯助剂ACR 和用作腈纶生产的第二单体,还可以用于生产涂料、粘合剂、润滑剂、纺织染料等。
MMA传统生产方法是以丙酮和氢氰酸为原料的丙酮氰醇法,但该工艺使用高毒、高腐蚀性的氢氰酸和硫酸,副产大量硫酸氢氨,因此对生产设备要求苛刻并对环境产生较大压力。上世纪八十年代以后,日本触媒、三菱人造丝和旭化成公司相继开发出以混合C4馏分中异丁烯/叔丁醇为原料制MMA生产工艺,由于该工艺环境污染小,产品成本低,很快成为目前全球第二大MMA生产工艺。近几年,英国Lucite公司开发出以乙烯、甲醇和CO为原料的MMA生产工艺,并于2007年在新加坡建立了工业装置。据该公司称:采用该工艺能够大幅度降低原料成本。但其技术成熟性和整体经济性有待进一步检验。
以异丁烯或叔丁醇为原料三步氧化生产甲基丙烯酸甲酯的工艺主要包括:一,异丁烯或叔丁醇在分子氧存在下气相催化氧化成甲基丙烯醛;二,甲基丙烯醛在分子氧存在下气相催化氧化成甲基丙烯酸;三,甲基丙烯酸与甲醇发生酯化反应生成甲基丙烯酸甲酯。目前,有关异丁烯或叔丁醇氧化合成甲基丙烯醛的专利已有大量报道,几乎所有专利都涉及到Mo、Bi、Fe三类元素,它们是催化剂必不可少的组分;而催化剂的改进主要是从催化剂的活性和稳定性方面进行的,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Fe、Co、Ni等元素以抑制Mo的升华,稳定催化剂活性组分,提高催化剂的使用寿命等。
对于异丁烯或叔丁醇选择氧化制甲基丙烯醛已有很多专利报道:
US Pat4250339、日本公开特许57-72937和CN1131059A中使用碲(Te)、铊(TI)等元素作为催化剂的关键部分,以提高催化剂的活性和选择性,但这些物质在催化剂的长期运转过程中易于飞散流失,从而造成催化剂的性能劣化。
US Pat5250485A提出通过改进催化剂的成分和它们的用量比例及催化剂制备方法,来提高异丁烯或叔丁醇转化率和目标产品收率。异丁烯转化率达到98.0%,甲基丙烯醛选择性85.3%,甲基丙烯酸选择性4.5%,甲基丙烯醛和甲基丙烯酸为总收率85.0%,仍不够理想。
JP Pat57-119837通过加入高分子化合物来控制催化剂表面结构,用于异丁烯或叔丁醇的选择氧化反应,但仍存在反应活性随反应时间降低的问题,需要进一步改进。
发明内容
本发明所要解决的技术问题是现有异丁烯或叔丁醇氧化制甲基丙烯醛的反应中甲基丙烯醛收率较低的问题,提供一种新的异丁烯或叔丁醇氧化制甲基丙烯醛方法。该方法用于异丁烯或叔丁醇选择氧化生产甲基丙烯醛反应中,具有异丁烯或叔丁醇转化率高、选择性好、甲基丙烯醛收率高的优点。
为解决上述技术问题,本发明中采用的技术方案如下:一种异丁烯或叔丁醇选择氧化合成甲基丙烯醛的方法,以异丁烯或叔丁醇和氧为原料,异丁烯或叔丁醇与氧的摩尔比为1:2~10,在反应温度为350~400℃,反应压力为0.1~0.12 Mpa,空速为800~1200 h-1,异丁烯或叔丁醇与水的摩尔比为1:1~4条件下,原料与催化剂接触,反应生成甲基丙烯醛,其中催化剂以选自SiO2或Al2O3中的至少一种为载体并含有由下列通式的活性组分Mo12BiaFebCocGedXeYfZgOx,式中a的取值范围为 0.05~6.0;b的取值范围为0.05~8.5;c的取值范围为0.05~15.0;d的取值范围为0.01~9.0;e的取值范围为0~5.0;f的取值范围为0.05~15.0;g的取值范围为0.01~5.0; X为选自W、V、Ni、Cr、Mn、Nb或Re中的至少一种;Y为选自Sn、Sr、Zn、Ti或Zr中的至少一种;Z为选自K、Rb、Na、Li、Tl或Cs中的至少一种,a、b、c、d、e、f和g分别代表元素铋、铁、钴、铈、X、Y和Z的原子比率,x为满足其它元素化合价所需的氧原子总数,催化剂中载体的用量为催化剂重量的5~40%,在催化剂制备过程中加入有机物作造孔剂,造孔剂选自草酸、尿素、聚乙烯醇、硬脂酸或季戊四醇中的至少一种。
上述技术方案中,异丁烯或叔丁醇与氧的摩尔比优选范围为1:2 ~5。催化剂的物理性能为:孔体积优选范围为≥0.20厘米3/克, 比表面积优选范围为≥12米2/克,孔径为0.05-0.1μm的孔径分布率优选范围为大于80%。
本发明方法中采用的催化剂的制备方法如下:
a)将制备催化剂所需量的钼酸铵溶解在水中,然后将制备催化剂所需量的载体硅溶胶、氧化铝或其混合物加入形成溶液Ⅰ;
b)将制备催化剂所需量的金属盐溶液溶解在水中形成溶液Ⅱ;
c)在搅拌下,将溶液Ⅱ加入溶液Ⅰ中形成催化剂浆料Ⅰ;
e)向浆料Ⅰ中加入所需量的造孔剂得浆料Ⅱ,造孔剂选自草酸、尿素、聚乙烯醇、硬脂酸或季戊四醇中的至少一种;
f)浆料Ⅱ通过喷雾或蒸发大部分水分后挤出成型得到催化剂前体,催化剂前体通过焙烧得到催化剂成品。
扩孔剂的加入量占催化剂重量的0.5-5%。
本发明发现此用于异丁烯或叔丁醇氧化制甲基丙烯醛的多组分复合氧化物催化剂。通过加入造孔剂可改善催化剂的物理性能,如孔体积、比表面积、及孔径分布,便可提高催化剂的选择性。同时Ge的加入用来稀释氧化物催化剂,提高催化剂的导热性能。采用本发明方法中的催化剂用于异丁烯或叔丁醇选择氧化制备甲基丙烯醛反应中,在异丁烯或叔丁醇与氧的摩尔比为1:2~10,在反应温度为350~400℃,反应压力为0.1~0.12 Mpa,空速为800~1200 h-1,异丁烯或叔丁醇与水的摩尔比为1:1~4条件下,其异丁烯或叔丁醇转化率可达98.5%,甲基丙烯醛及甲基丙烯酸选择性可达92.5%,产物甲基丙烯醛及甲基丙烯酸收率可达91.1%,取得了较好的技术效果。
下面通过实施例对本发明作进一步阐述。
具体实施方式
【比较例】
将100克 (NH4)6Mo7O24·4H2O 加入到100克 70℃的温水中,搅拌使其全部溶解,加入63.2克 40%(wt.)的硅溶胶制成物料A。
将 38.5克 Fe(NO3)3·9H2O加入到20克的70℃热水中,搅拌溶解后再加入34.3克 Bi(NO3)3·5H2O、41.2克Co(NO3)2·6H2O、25.1克 Mn(NO3)2溶液(50%)、0.3克Zn(NO3)2·6H2O、0.5克CsNO3搅拌溶解后制成物料B。
将溶液B加入溶液A中,形成催化剂浆料, 在80℃下搅拌老化2小时,浆料120℃烘干去除大部分水分后挤出成型,得到φ3.5x3.5mm的圆柱状物,然后高温焙烧得到催化剂成品,焙烧温度为400℃~550℃。该催化剂组成及制备条件列于表1,在异丁烯与氧的摩尔比为1:2;在反应温度为350℃;反应压力为0.1 Mpa; 空速为1000 h-1;异丁烯与水的摩尔比为1:2条件下考评,其结果列于表2。
【实施例1】
将100 克 (NH4)6Mo7O24·4H2O加入到100克 70℃的温水中,搅拌使其全部溶解,加入89.4克 40%(wt.)的硅溶胶、35.8克20%铝溶胶和19.1克 (NH4)6H5[H2(WO4)6]制成物料A。
将 38.5克 Fe(NO3)3·9H2O加入到20克的70℃热水中,搅拌溶解后再加入34.3克 Bi(NO3)3·5H2O、41.2克Co(NO3)2·6H2O、6.1克 Ce(NO3)3·6H2O、0.7克Zn(NO3)2·6H2O、0.3克CsNO3搅拌溶解后制成物料B。
将溶液B加入溶液A中,形成催化剂浆料,加入草酸5.13克,并在80℃下搅拌老化2小时,浆料120℃烘干去除大部分水分后挤出成型,得到φ3.5x3.5mm的圆柱状物,然后高温焙烧得到催化剂成品,焙烧温度为400℃~550℃。该催化剂组成及制备条件列于表1,在异丁烯与氧的摩尔比为1:2;在反应温度为350℃;反应压力为0.1 Mpa; 空速为1000 h-1;异丁烯与水的摩尔比为1:2条件下考评,其结果列于表2。
【实施例2】
将100 克 (NH4)6Mo7O24·4H2O加入到100克 70℃的温水中,搅拌使其全部溶解,加入78.9克 40%(wt.)的硅溶胶、47.7克20%铝溶胶和8.24克NH4VO3制成物料A。
将 38.5克 Fe(NO3)3·9H2O加入到20克的70℃热水中,搅拌溶解后再加入34.3克 Bi(NO3)3·5H2O、41.2克Co(NO3)2·6H2O、6.1克 Ce(NO3)3·6H2O、0.7克Zn(NO3)2·6H2O、0.5克CsNO3搅拌溶解后制成物料B。
将溶液B加入溶液A中,形成催化剂浆料,加入尿素5.13克,并在80℃下搅拌老化2小时,浆料120℃烘干去除大部分水分后挤出成型,得到φ3.5x3.5mm的圆柱状物,然后高温焙烧得到催化剂成品,焙烧温度为400℃~550℃。该催化剂组成及制备条件列于表1,在叔丁醇与氧的摩尔比为1:2;在反应温度为350℃;反应压力为0.1 Mpa; 空速为1000 h-1;叔丁醇与水的摩尔比为1:2条件下考评,其结果列于表2。
【实施例3~11】
按实施2的各个步骤制得催化剂,具体结果列于表1。在与实施例2相同的评价条件下,反应结果列于表2。
【实施例12~21】
在不同的反应条件下对实施例1催化剂的考评结果列于表3。
表1 催化剂重量组成及制备条件
表2 催化剂评价结果
表3 不同反应条件下催化剂评价结果2
Claims (3)
1.一种异丁烯或叔丁醇选择氧化合成甲基丙烯醛的方法,以异丁烯或叔丁醇和氧为原料,异丁烯或叔丁醇与氧的摩尔比为1:2~10,在反应温度为350~400℃,反应压力为0.1~0.12 Mpa,空速为800~1200 h-1,异丁烯或叔丁醇与水的摩尔比为1:1~4条件下,原料与催化剂接触,反应生成甲基丙烯醛,其中催化剂以选自SiO2或Al2O3中的至少一种为载体并含有由下列通式的活性组分Mo12BiaFebCocGedXeYfZgOx,式中a的取值范围为 0.05~6.0;b的取值范围为0.05~8.5;c的取值范围为0.05~15.0;d的取值范围为0.01~9.0;e的取值范围为0~5.0;f的取值范围为0.05~15.0;g的取值范围为0.01~5.0; X为选自W、V、Ni、Cr、Mn、Nb或Re中的至少一种;Y为选自Sn、Sr、Zn、Ti或Zr中的至少一种;Z为选自K、Rb、Na、Li、Tl或Cs中的至少一种,a、b、c、d、e、f和g分别代表元素铋、铁、钴、铈、X、Y和Z的原子比率,x为满足其它元素化合价所需的氧原子总数,催化剂中载体的用量为催化剂重量的5~40%,在催化剂制备过程中加入有机物作造孔剂,造孔剂选自草酸、尿素、聚乙烯醇、硬脂酸或季戊四醇中的至少一种。
2.根据权利要求书1所述的异丁烯或叔丁醇选择氧化合成甲基丙烯醛的方法,其特征在于异丁烯或叔丁醇与氧的摩尔比为1:2 ~5。
3.根据权利要求书1所述的异丁烯或叔丁醇选择氧化合成甲基丙烯醛的方法,其特征在于催化剂的物理性能为:孔体积≥0.20厘米3/克, 比表面积≥12米2/克,孔径为0.05-0.1μm的孔径分布率大于80%。
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