CN108620084A - 一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂及其制备方法 - Google Patents
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂及其制备方法 Download PDFInfo
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
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- 150000004703 alkoxides Chemical class 0.000 claims 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
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- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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Abstract
本发明涉及一种催化剂及其制备方法,特别涉及一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂及其制备方法。所述催化剂为体相催化剂,所述催化剂的金属活性组分为镍和钼,所述镍和钼的摩尔比为8~32:1。所述催化剂的比表面积大于50m2/g,孔容在0.1~0.8mL/g。本发明的催化剂催化活性高、可以在常压、较低的反应温度下高效地将硝基苯转化为苯胺。同时,本发明催化剂的主要成分为常规的过渡金属,成本低,并且制备过程简单,易于工业化生产。
Description
技术领域
本发明涉及一种催化剂及其制备方法,特别涉及一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂及其制备方法。
背景技术
苯胺又称阿尼林油,是一种重要的化工产品和有机化工原料,在化工生产中主要用于生产聚氨酯原料二苯基甲烷二异氰酸酯(MDI),在染料行业、医药工业、农药行业中有诸多应用,由其制得的化工产品和中间体有300多种。
目前,工业上苯胺的生产方法大致分为三种:硝基苯铁粉还原法、苯酚直接氨化法和硝基苯催化加氢法。硝基苯铁粉还原法和苯酚直接氨化法由于存在制备成本高,产生大量废水、废渣,不符合“绿色化学”要求等诸多弊端。因此,硝基苯催化加氢法作为绿色清洁生产工艺,已是目前苯胺生产的主流方法。硝基苯催化加氢分为液相加氢和气相加氢。气相加氢反应通常需要较高的反应温度和氢压,能耗大,对设备要求高,操作危险性大。而液相加氢工艺,以其较低的反应温度,能够减少副反应,延长催化剂使用寿命,且转化率高,设备投资小等优点越来越成为研究的热点。
硝基苯液相加氢制备苯胺的催化剂主要是Pt、Pd和Rh等贵金属负载在氧化铝和活性炭等载体上的贵金属催化剂,以及负载型镍、铜,纳米和非晶态合金催化剂等。然而,这些催化剂存在着价格昂贵、反应压力高、抗毒性差、生产步骤繁琐等诸多问题。因此,现在市场上亟需一种催化活性高、选择性好、可以在常压、较低的反应温度下将硝基苯转化为苯胺,同时制备过程简单,成本低,易于工业化生产的催化剂及其制备方法。
发明内容
为解决现有技术存在的不足,本发明提供一种催化活性高、可以在常压、较低的反应温度下,高效地将硝基苯转化为苯胺,同时制备过程简单,成本低,易于工业化生产的体相镍钼催化剂及其制备方法。
本发明的技术方案为:
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂,所述催化剂为体相催化剂,所述催化剂的金属活性组分为镍和钼,所述镍和钼的摩尔比为8~32:1,所述催化剂的比表面积大于50m2/g,孔容在0.1~0.8mL/g。
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,包括如下步骤:
(1)配制0.8~1.8mol/L硝酸镍水溶液,按照每升所述硝酸镍水溶液以100~300g的量加入聚乙二醇,搅拌溶解。
(2)配制沉淀剂1和沉淀剂2混合水溶液,所述沉淀剂1和沉淀剂2的摩尔比为2~4:1,所述沉淀剂混合水溶液总浓度为1~2mol/L。
(3)边搅拌边缓慢将步骤(2)配制的混合水溶液加入到步骤(1)配制的硝酸镍与聚乙二醇混合溶液中,直至完全反应不再有沉淀生成为止,得到悬浮液。
(4)将步骤(3)得到的悬浮液转移至高压釜中,按照镍和钼的摩尔比为8~32:1加入七钼酸铵[(NH4)6Mo7O24·4H2O],搅拌溶解后,密闭高压釜,边搅拌边在130~180℃下保持3~8h。
(5)步骤(4)反应完成后,自然降温,将悬浮液过滤,所得沉淀物用水和无水乙醇洗涤,然后进行干燥,干燥后,在300~420℃煅烧2~6h,即得到催化剂前驱体。
(6)将步骤(5)得到的催化剂前驱体在氢气气氛下,350~450℃还原2~8h,降至室温后,用含1%O2的N2钝化1~3h,备用,所述1%为质量百分比。
优选的,所述步骤(1)中聚乙二醇为分子量为300~1600的聚乙二醇。
优选的,所述步骤(1)中聚乙二醇为分子量为300、800、1000、1600的聚乙二醇中的任意一种或几种。
优选的,所述步骤(2)中沉淀剂1为碳酸钠或碳酸钾,所述沉淀剂2为氢氧化钠或氢氧化钾。
优选的,所述步骤(4)中加热时间为4h。
优选的,所述步骤(5)中在60℃和120℃下各干燥2h。
优选的,所述步骤(5)中煅烧时间为3h。
优选的,所述步骤(6)中还原温度为375℃。
本发明所达到的有益效果为:
本发明的催化剂催化活性高,可以在常压、较低的反应温度下将硝基苯转化为苯胺。同时,本发明催化剂的主要成分为常规的过渡金属,成本低,并且制备过程简单,易于工业化生产。
附图说明
图1是本发明实施例2体相镍钼催化剂的扫描电镜(SEM)图。
具体实施方式
为便于本领域的技术人员理解本发明,下面结合实施例说明本发明的具体实施方式。
实施例1
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,包括如下步骤:
(1)配制1升0.8mol/L硝酸镍水溶液,加入100g聚乙二醇300,搅拌溶解。
(2)配制碳酸钠和氢氧化钠混合水溶液,其中碳酸钠浓度0.8mol/L、氢氧化钠浓度为0.4mol/L。
(3)边搅拌边缓慢将步骤(2)配制的混合溶液加入到步骤(1)配制的混合溶液中,直至完全反应不再有沉淀生成为止,得到悬浮液。
(4)将步骤(3)得到的悬浮液转移至高压釜中,加入0.0143mol四水七钼酸铵,搅拌溶解后,密闭高压釜,开启搅拌,升温至130℃下加热5h。
(5)步骤(4)反应完成后,将悬浮液过滤,所得沉淀物用水和无水乙醇洗涤,在60℃和120℃下各干燥2h后,在350℃煅烧2h,得到催化剂前驱体。
(6)将步骤(5)得到的催化剂前驱体在氢气气氛下,350℃还原8h,降至室温后,再用为含1%(质量百分比)O2的N2钝化1h,备用。
由上述制备方法制备的催化剂,镍和钼的摩尔比为8:1,所述催化剂的比表面积、孔容和平均孔径如表1所示。
实施例2
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,包括如下步骤:
(1)配制1升0.8mol/L硝酸镍水溶液,加入100g聚乙二醇300,搅拌溶解。
(2)配制碳酸钠和氢氧化钠混合水溶液,其中碳酸钠浓度0.8mol/L、氢氧化钠浓度为0.4mol/L。
(3)边搅拌边缓慢将步骤(2)配制的混合溶液加入到步骤(1)配制的混合溶液中,直至完全反应不再有沉淀生成为止,得到悬浮液。
(4)将步骤(3)得到的悬浮液转移至高压釜中,加入0.011mol四水七钼酸铵,搅拌溶解后,密闭高压釜,开启搅拌,升温至130℃下加热5h。
(5)步骤(4)反应完成后,将悬浮液过滤,所得沉淀物用水和无水乙醇洗涤,在60℃和120℃下各干燥2h后,在350℃煅烧2h,得到催化剂前驱体。
(6)将步骤(5)得到的催化剂前驱体在氢气气氛下,350℃还原8h,降至室温后,再用为含1%(质量百分比)O2的N2钝化1h,备用。
由上述制备方法制备的催化剂,镍和钼的摩尔比为10.7:1,所述催化剂的比表面积、孔容和平均孔径如表1所示。
实施例3
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,包括如下步骤:
(1)配制1升0.8mol/L硝酸镍水溶液,加入100g聚乙二醇300,搅拌溶解。
(2)配制碳酸钠和氢氧化钠混合水溶液,其中碳酸钠浓度0.8mol/L、氢氧化钠浓度为0.4mol/L。
(3)边搅拌边缓慢将步骤(2)配制的混合溶液加入到步骤(1)配制的混合溶液中,直至完全反应不再有沉淀生成为止,得到悬浮液。
(4)将步骤(3)得到的悬浮液转移至高压釜中,加入0.0071mol四水七钼酸铵,搅拌溶解后,密闭高压釜,开启搅拌,升温至130℃下加热5h。
(5)步骤(4)反应完成后,将悬浮液过滤,所得沉淀物用水和无水乙醇洗涤,在60℃和120℃下各干燥2h后,在350℃煅烧2h,得到催化剂前驱体。
(6)将步骤(5)得到的催化剂前驱体在氢气气氛下,350℃还原8h,降至室温后,再用为含1%(质量百分比)O2的N2钝化1h,备用。
由上述制备方法制备的催化剂,镍和钼的摩尔比为16:1,所述催化剂的比表面积、孔容和平均孔径如表1所示。
实施例4
一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,包括如下步骤:
(1)配制1升0.8mol/L硝酸镍水溶液,加入100g聚乙二醇300,搅拌溶解。
(2)配制碳酸钠和氢氧化钠混合水溶液,其中碳酸钠浓度0.8mol/L、氢氧化钠浓度为0.4mol/L。
(3)边搅拌边缓慢将步骤(2)配制的混合溶液加入到步骤(1)配制的混合溶液中,直至完全反应不再有沉淀生成为止,得到悬浮液。
(4)将步骤(3)得到的悬浮液转移至高压釜中,加入0.0036mol四水七钼酸铵,搅拌溶解后,密闭高压釜,开启搅拌,升温至130℃下加热5h。
(5)步骤(4)反应完成后,将悬浮液过滤,所得沉淀物用水和无水乙醇洗涤,在60℃和120℃下各干燥2h后,在350℃煅烧2h,得到催化剂前驱体。
(6)将步骤(5)得到的催化剂前驱体在氢气气氛下,350℃还原8h,降至室温后,再用为含1%(质量百分比)O2的N2钝化1h,备用。
由上述制备方法制备的催化剂,镍和钼的摩尔比为32:1,所述催化剂的比表面积、孔容和平均孔径如表1所示。
表1实施例1-4制备的催化剂的比表面积、孔容和平均孔径
催化剂 | 比表面积(m2/g) | 孔容(mL/g) | 平均孔径(nm) |
实施例1 | 63.4 | 0.43 | 17.3 |
实施例2 | 83.2 | 0.46 | 12.2 |
实施例3 | 54.8 | 0.22 | 30.4 |
实施例4 | 34.4 | 0.10 | 4.3 |
试验例
实施例1-4中催化剂催化硝基苯的加氢制苯胺,反应步骤如下:
将10g催化剂前驱体放入固定床反应器中,在20ml/min的H2流量下,400℃活化1h。活化完成后,调整反应在100℃,用进料泵将硝基苯泵入反应器,原料质量空速1h-1,氢气流量250ml/min,压力为常压。反应产物经冷凝后用配SE-3毛细管柱的岛津GC2010plus分析组成,结果见表2。
表2实施例1-4制备的催化剂的催化性能
催化剂 | 硝基苯转化率(%) | 苯胺选择性(%) |
实施例1 | 83.4 | 99 |
实施例2 | 98.0 | 99 |
实施例3 | 76.9 | 97 |
实施例4 | 54.6 | 92 |
由表2中结果可知,本发明提供的催化剂可以在极其温和的条件下,将硝基苯转化为苯胺,反应中的副产物,像亚硝基苯、N-苯基羟胺、偶氮苯等含量较少,催化剂选择性高。
以上所述的本发明实施方式,并不构成对本发明保护范围的限定。任何在本发明的精神和原则之内所作的修改、等同替换和改进等,均应包含在本发明的权利要求保护范围之内。
Claims (10)
1.一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂,其特征在于:所述催化剂为体相催化剂,所述催化剂的金属活性组分为镍和钼,所述镍和钼的摩尔比为8~32:1。
2.根据权利要求1所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂,其特征在于:所述催化剂的比表面积大于50m2/g,所述催化剂的孔容在0.1~0.8mL/g。
3.根据权利要求1所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于,包括如下步骤:
(1)配制0.8~1.8mol/L硝酸镍水溶液,按照每升所述硝酸镍水溶液以100~300g的量加入聚乙二醇,搅拌溶解;
(2)配制沉淀剂1和沉淀剂2混合水溶液,所述沉淀剂1和沉淀剂2的摩尔比为2~4:1,所述沉淀剂混合水溶液总浓度为1~2mol/L;
(3)边搅拌边缓慢将步骤(2)配制的混合水溶液加入到步骤(1)配制的硝酸镍与聚乙二醇混合溶液中,直至完全反应不再有沉淀生成为止,得到悬浮液;
(4)将步骤(3)得到的悬浮液转移至高压釜中,按照镍和钼的摩尔比为8~32:1加入七钼酸铵,搅拌溶解后,密闭高压釜,边搅拌边在130~180℃下保持3~8h;
(5)步骤(4)反应完成后,自然降温,将悬浮液过滤,所得沉淀物用水和无水乙醇洗涤,然后进行干燥,干燥后,在300~420℃煅烧2~6h,即得到催化剂前驱体;
(6)将步骤(5)得到的催化剂前驱体在氢气气氛下,350~450℃还原2~8h,再在室温下,用含1%O2的N2钝化1~3h,备用,所述1%为质量百分比。
4.根据权利要求3所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(1)中聚乙二醇为分子量为300~1600的聚乙二醇。
5.根据权利要求4所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(1)中聚乙二醇为分子量为300、800、1000、1600的聚乙二醇中的任意一种或几种。
6.根据权利要求3所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(2)中沉淀剂1为碳酸钠或碳酸钾,所述沉淀剂2为氢氧化钠或氢氧化钾。
7.根据权利要求3所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(4)中加热时间为4h。
8.根据权利要求3所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(5)中在60℃和120℃下各干燥2h。
9.根据权利要求3所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(5)中煅烧时间为3h。
10.根据权利要求3所述的一种用于硝基苯液相加氢制苯胺的体相镍钼催化剂的制备方法,其特征在于:所述步骤(6)中还原温度为375℃。
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