CN102029158A - 一种硫化型加氢催化剂材料及其制备方法 - Google Patents
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Abstract
本发明公开了一种硫化型加氢催化材料及其制备方法,属于石油化工炼油工业技术中催化材料制备技术领域。本发明的技术方案是:首先利用常见的类水滑石材料的制备方法水热合成方法在载体上原位制备出层状双羟基复合金属氧化物,即类水滑石前体,可通过调变金属离子浓度,制备出负载量不同的类水滑石前体;经焙烧后,得到类水滑石催化剂前体;在旋转蒸发仪中液相硫化催化剂前体,得到硫化型加氢催化剂材料。采用本发明提供的方法制备高分散负载型加氢催化材料,其制备方法简便,效果良好,适宜工业化生产。
Description
技术领域
本发明涉及石油化工炼油工业技术中催化材料制备技术领域,尤其是催化加氢技术中加氢催化剂的制备及硫化处理工艺。
背景技术
近年来,随着世界石油储量减少,原油重质化趋势日益明显,原油中硫、氮、金属等含量增加,为了充分利用有限资源,炼油工业需要更有效的脱除技术;而且目前世界大城市污染严重,空气质量越来越差,对机动车辆排放废气中的NOx、SOx及芳烃含量等的限制更加苛刻;加氢技术是生产清洁燃料、减轻环境污染的有效措施之一,由于这些原因,使得加氢技术成为炼油工业中非常重要的加工环节,因此开发具有高活性和选择性的加氢催化剂受到了人们的广泛关注。
工业上使用的加氢催化剂,大多采用Mo、Co、Ni、W等金属元素作活性组分,并以氧化态分散在多孔载体上。大量的研究表明,这种形态的催化剂加氢活性低、稳定性差。在加氢运转过程中,虽由于原料油中含有硫化物,催化剂可通过反应而转化为硫化态,但往往由于在反应条件下,原料油含硫量过低,硫化不完全而导致一部分金属还原,使催化剂活性达不到正常水平。实验证明,只有将催化剂进行预处理,将金属氧化态转化为硫化态,才能表现出较高的活性。
因此,加氢催化剂在使用前必须进行预硫化。早在1930年,石脑油加氢脱硫装置首次采用预硫化,1950年后,重油加氢装置也开始对催化剂进行预硫化处理。良好的预硫化技术能够使加氢催化剂保持最佳的加氢活性和稳定性,提高催化剂的选择性,延长催化剂的使用寿命,是使催化剂得到最大程度利用的有效措施。
综观现有技术,都存在这样那样的不足,因此需要新的技术来克服。
发明内容
本发明的目的在于提供一种硫化型加氢催化剂材料及其制备方法,即使用层状前体法在载体上合成类水滑石,实现将具有较好催化加氢性能的VIII族和VIB族金属负载到载体上,最后进行预硫化处理。
本发明的技术方案是:1).首先利用常见的类水滑石材料的制备方法水热合成方法在载体上原位制备出层状双羟基复合金属氧化物,即类水滑石前体,可通过调变金属离子浓度,制备出负载量不同的类水滑石前体;2).经焙烧后,得到类水滑石催化剂前体;3).在旋转蒸发仪中液相硫化催化剂前体,得到硫化型加氢催化剂材料。
本发明的具体制备步骤如下:
A、将3-10g经过450-950℃焙烧4-6小时的载体加入到100-1000ml混合盐溶液中,该混合盐溶液中金属离子浓度为0.05-0.35mol/l,边搅拌边逐滴添加1-5wt%的稀氨水溶液,调节溶液pH值在7-8之间;然后置于50-90℃的水浴振荡器中,振荡频率为100-200次/min,水热晶化12-36小时,即在载体表面原位生长出类水滑石;
B、倒掉上层澄清液,用去离子水洗涤表面原位生长类水滑石的载体至pH值为7-8,于真空干燥箱中50-180℃干燥12-24小时,经450-600℃焙烧4-6小时,得到类水滑石催化剂前体;
C、将3-8g经焙烧处理的类水滑石催化剂前体转移至旋转蒸发仪中,先抽真空30-1200min,再加入10-50ml经烷烃稀释的硫化剂,真空旋转蒸发至烷烃挥发完全;
D、重复C步骤1-5次,经干燥即得硫化型加氢催化剂。
所述的混合盐溶液含有元素周期表中VIII族和VIB族中的一种或几种金属离子,还含有NH4NO3或尿素,金属离子与NH4NO3或尿素的比例范围为1∶10-1∶3。
所述的硫化剂是指液体含硫化合物,具体为二甲基硫醚、二甲基二硫醚、硫醇或硫醚中的一种或者几种;烷烃具体为甲苯和/或正庚烷;经烷烃稀释后硫的质量百分含量为2.5-50%。
所述的载体为氧化铝、氧化钛、沸石、活性炭、氧化锆、粘土、渗铝水泥或硅藻土。
本发明的显著特点在于借助于水滑石的晶格特性,将具有较高加氢活性的VIII族和VIB族金属以高分散的状态均匀负载到载体上。采用本发明提供的方法制备高分散负载型加氢催化材料,其制备方法简便,效果良好,适宜工业化生产。
附图说明
图1为氧化铝小球(a)、传统浸渍法所得催化剂前体(b)及实施例1所获得的表面原位生长类水滑石的氧化铝小球(c)的XRD谱图;
图2为氧化铝小球(a)、传统浸渍法所得催化剂前体(b)、实施例1所获得的表面原位生长类水滑石的氧化铝小球(c)及预硫化后所得硫化型加氢催化剂(d)的XRD谱图;
图3为实例1所得硫化型加氢催化剂(a),传统浸渍法所得催化剂(b),实施例3所得硫化型加氢催化剂(c)的程序升温还原图。
具体实施方式
下面结合实施例对本发明作进一步的描述:
实施例1
A:称取8.72gNi(NO3)2·6H2O和14.55gNH4NO3溶解在200mL去离子水中,配成混合盐溶液;然后再称取6g经过800℃焙烧6小时的氧化铝小球,加入到上述混合盐溶液中;边搅拌边逐滴添加2wt%的稀氨水溶液,调节溶液pH值在7.25;然后置于70℃的水浴振荡器中,振荡频率为140次/min,水热晶化24小时,得上层澄清液和下层浅绿色小球,即在氧化铝小球表面原位生长出类水滑石;
B:检测上层澄清液几乎不含多余的Ni2+;倒掉上层澄清液,用去离子水洗涤下层浅绿色小球至中性,转移至真空干燥箱,于70℃下干燥12小时,经500℃焙烧4小时即得类水滑石催化剂前体;
C:将5g经焙烧处理的类水滑石催化剂前体转移至旋转蒸发仪中,先抽真空40min,然后加入20mL经正庚烷稀释的硫化剂,其中硫的质量百分含量为10%,真空旋转蒸发至正庚烷挥发完全;
D、重复C步骤硫化过程2次,经干燥即得硫化型加氢催化剂。
实施例2
A:同实例1;
B:同实例1;
C:将5g经焙烧处理的类水滑石催化剂前体转移至旋转蒸发仪中,先抽真空40min,然后加入20mL经正庚烷稀释的硫化剂,其中硫的质量百分含量为7.5%,真空旋转蒸发至正庚烷挥发完全;
D:重复C步骤硫化过程2次,经干燥即得硫化型加氢催化剂。
实施例3
A:称取4.65gNi(NO3)2·6H2O和7.76gNH4NO3溶解在去离子水中,配成混合盐溶液;然后再称取6g经650℃焙烧5小时的氧化铝小球,加入到上述混合盐溶液中;边搅拌边逐滴添加事先准备好的2wt%的稀氨水溶液,调节溶液pH值在7.25,最后溶液体积保持200mL;然后置于50℃的水浴振荡器中,保持温度在50℃,振荡频率为140次/min,水热晶化24小时,得上层澄清液和下层浅绿色小球,即在氧化铝小球表面原位生长出类水滑石;
B:检测上层澄清液几乎不含多余的Ni2+;倒掉上层澄清液,用去离子水洗涤下层浅绿色小球至中性,转移至真空干燥箱,于70℃下干燥12小时,经500℃焙烧4小时即得类水滑石催化剂前体;
C:将5g经焙烧处理的类水滑石催化剂前体转移至旋转蒸发仪中,先抽真空40min,然后加入20mL经正庚烷稀释的硫化剂,其中硫的质量百分含量为10%,真空旋转蒸发至正庚烷完全挥发;
D:重复C步骤硫化过程2次,经干燥即得硫化型加氢催化剂。
实施例4
A:同实例3;
B:同实例3;
C:将5g经焙烧处理的类水滑石催化剂前体转移至旋转蒸发仪中,先抽真空40min,然后加入20mL经正庚烷稀释的硫化剂,其中硫的质量百分含量为8.5%,真空旋转蒸发至正庚烷完全挥发;
D:重复C步骤硫化过程2次,经干燥即得硫化型加氢催化剂。
传统浸渍法实施方案
A:称取6g经过800℃焙烧6小时的氧化铝小球,置于50ml,浓度0.15mol/L的Ni(NO3)2水溶液中,在70℃的温度下,蒸发30-60min至基本无水为止;将温度升高至90℃,继续蒸发30min,以使水分进一步脱除;蒸发后样品在70℃烘箱中干燥24h,然后经500℃焙烧4小时得到催化剂前体;
B:将5g催化剂前体转移至旋转蒸发仪中,先抽真空40min,然后加入20mL经正庚烷稀释的硫化剂,其中硫的质量百分含量为8.5%,真空旋转蒸发至正庚烷完全挥发;
C:重复B步骤硫化过程2次,经干燥即得硫化型加氢催化剂。
采用Shimadu XRD-6000型粉末X射线衍射仪对制备的产物进行定性分析,结果如下:
图1为氧化铝小球、传统浸渍法所得催化剂前体及实施例1所获得的表面原位生长类水滑石的氧化铝小球的XRD谱图。球形氧化铝载体γ-Al2O3的XRD谱图如图的曲线a所示。从图中可以看出,γ-Al2O3载体相对于晶面311、400和440特征衍射峰的2θ分别出现在37.05°、45.90°和66.83°,对应的晶面间距d311、d400和d440分别为0.242nm、0.197nm和0.140nm。这与文献报道的γ-Al2O3的晶体衍射峰的位置一致。
图2列出了原位合成法制备得到的NiAl-LDHs/γ-Al2O3,即表面原位生长类水滑石的氧化铝小球c和浸渍法制备得到的催化剂前体b的XRD谱图。为了进行对比也同时列出了载体γ-Al2O3的XRD谱图。从图中可以看出NiAl-LDHs/γ-Al2O3催化剂前体除了载体γ-Al2O3的特征衍射峰以外,还分别在2θ为11.0°、22.2°和60.8°处出现了反映LDHs晶体结构的003、006和110晶面特征衍射峰。而传统浸渍法得到的催化剂前体就没有LDHs的特征衍射峰。由此可以证明原位合成法制得的NiAl-LDHs/γ-Al2O3催化剂前体具有LDHs的晶体结构。图2中曲线d为实施例1催化剂前体经焙烧、预硫化后所得催化剂的XRD谱图。可以明显的看出经焙烧后,催化剂前体已经失去水滑石的层状结构,不过,它并不影响原来镍的位置,因此能维持镍良好的分散状态。同时由于上硫量较低,硫的特征衍射峰并不明显。
催化剂程序升温还原测定在天津先权仪器公司生产的TP5000多用吸附仪上进行,结果如下:
图3为实例1所得硫化型加氢催化剂a,传统浸渍法所得催化剂b,实例3所得硫化型加氢催化剂c的程序升温还原图。由图中可以看出,曲线a的最高还原温度为572℃,曲线b的最高还原温度为548℃,曲线c的最高还原温度为559℃。最大还原温度越高表明物种越难还原,所以原位法所得催化剂比浸渍法所得到的催化剂难还原。这是由于原位法制备的催化剂物种中原子间相互作用大引起的。
Claims (5)
1.一种硫化型加氢催化剂材料的制备方法,其特征在于,其具体步骤如下:
A、将3-10g经过450-950℃焙烧4-6小时的载体加入到100-1000ml混合盐溶液中,该混合盐溶液中金属离子浓度为0.05-0.35mol/l,边搅拌边逐滴添加1-5wt%的稀氨水溶液,调节溶液pH值在7-8之间;然后置于50-90℃的水浴振荡器中,振荡频率为100-200次/min,水热晶化12-36小时,即在载体表面原位生长出类水滑石;
B、倒掉上层澄清液,用去离子水洗涤表面原位生长类水滑石的载体至pH值为7-8,于真空干燥箱中50-180℃干燥12-24小时,经450-600℃焙烧4-6小时,得到类水滑石催化剂前体;
C、将3-8g经焙烧处理的类水滑石催化剂前体转移至旋转蒸发仪中,先抽真空30-1200min,再加入10-50ml经烷烃稀释的硫化剂,真空旋转蒸发至烷烃挥发完全;
D、重复C步骤1-5次,经干燥即得硫化型加氢催化剂。
2.根据权利要求1所述的一种硫化型加氢催化剂材料的制备方法,其特征在于,所述的混合盐溶液含有元素周期表VIII族和VIB族中的一种或几种金属离子,还含有NH4NO3或尿素,金属离子与NH4NO3或尿素的比例范围为1∶10-1∶3。
3.根据权利要求1或2所述的一种硫化型加氢催化剂材料的制备方法,其特征在于,所述的硫化剂是指液体含硫化合物,具体为二甲基硫醚、二甲基二硫醚、硫醇或硫醚中的一种或者几种;烷烃具体为甲苯和/或正庚烷;经烷烃稀释后硫的质量百分含量为2.5-50%。
4.根据权利要求1或2所述的一种硫化型加氢催化剂材料的制备方法,其特征在于,所述的载体为氧化铝、氧化钛、沸石、活性炭、氧化锆、粘土、渗铝水泥或硅藻土。
5.根据权利要求3所述的一种硫化型加氢催化剂材料的制备方法,其特征在于,所述的载体为氧化铝、氧化钛、沸石、活性炭、氧化锆、粘土、渗铝水泥或硅藻土。
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CN103627424A (zh) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | 一种渣油加氢脱氮的方法 |
CN104148064A (zh) * | 2014-06-19 | 2014-11-19 | 北京化工大学 | 一种活性中心高分散的负载型双金属催化剂的制备方法 |
CN104646007B (zh) * | 2013-11-22 | 2017-03-15 | 中国石油天然气股份有限公司 | 一种渣油加氢脱金属催化剂及其制备和应用 |
CN109433179A (zh) * | 2018-11-29 | 2019-03-08 | 西安科技大学 | 一种花苞状水滑石-活性炭复合光催化剂的制备方法 |
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CN103627424A (zh) * | 2012-08-23 | 2014-03-12 | 中国石油天然气股份有限公司 | 一种渣油加氢脱氮的方法 |
CN104646007B (zh) * | 2013-11-22 | 2017-03-15 | 中国石油天然气股份有限公司 | 一种渣油加氢脱金属催化剂及其制备和应用 |
CN104148064A (zh) * | 2014-06-19 | 2014-11-19 | 北京化工大学 | 一种活性中心高分散的负载型双金属催化剂的制备方法 |
CN104148064B (zh) * | 2014-06-19 | 2016-03-30 | 北京化工大学 | 一种活性中心高分散的负载型双金属催化剂的制备方法 |
CN109433179A (zh) * | 2018-11-29 | 2019-03-08 | 西安科技大学 | 一种花苞状水滑石-活性炭复合光催化剂的制备方法 |
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