CN108722454A - 一种煤焦油加氢脱金属催化剂及其制备方法 - Google Patents
一种煤焦油加氢脱金属催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种煤焦油加氢脱金属催化剂及其制备方法,包括氧化铝载体和加氢活性组分组成,本发明制备的煤焦油加氢脱金属催化剂,在载体制备过程采用了冷冻干燥法,通过冻结、升华和再干燥三个阶段,与其他干燥方法相比,干燥后的载体能够保持挤条成型后的原有框架结构。在载体焙烧过程中将Si引入到Al‑O键形成的网络中,打断了Al‑O键间的联接,形成断网,降低了表面张力,孔壁塌陷导致孔径增大,能够直接有效的控制氧化铝载体的孔结构;所制备的催化剂是将氧化铝表面羟基缩合,降低载体的酸性,提高加氢脱金属催化剂反应稳定性。通过扩孔剂和烧结剂的双重作用,氧化铝载体孔容大,孔分布集中,且机械强度较高,具有适宜的表面酸性。
Description
技术领域:
本发明涉及一种加氢脱金属催化剂及其制备方法,尤其是用于煤焦油加氢脱金属的催化剂及其制备方法。
背景技术:
目前世界经济高速发展,对燃料油品的需求越来越多,世界原油资源的短缺迫在眉睫,而煤炭的储存量却非常丰富,因此使用煤炭来生产车用燃料油品是一种途径,由煤制油的主要技术包括煤的直接液化和煤的间接液化等,但这些技术成本高,技术复杂。另外一种生产焦炭的技术,可以在生产焦炭的同时,副产煤焦油,这是目前广泛采用的方法。煤焦油的传统加工方法以物理分离、提取单组分或窄馏分产品为目标,中温煤焦油除提取粗酚等少量化工产品外,大多作为燃料直接利用。传统加工方法,既不具备经济性,也不具备清洁性,煤焦油大部分只能简单的直接作燃料用,因硫氮含量高和不能完全燃烧,造成严重的环境污染,市场价值极低。
煤焦油加氢技术能够有效的解决传统煤焦油加工过程存在的弊端,煤焦油中含有大量的金属杂质,要求加氢脱金属剂具有较大的孔容和孔径,现有的加氢脱金属剂一般采用孔径较大的氧化铝作为载体基质,但是常规的方法制备的氧化铝孔径大小难以满足使用要求,通常需要采用扩孔的办法来实现。
US444896公开了一种渣油加氢脱金属催化剂的制备方法,该催化剂以至少一种Ⅷ和/或ⅥB族金属元素为活性组分,负载在大孔径氧化铝载体上。制备方法是将拟薄水铝石与炭黑粉混捏均匀,成型、干燥,在含氧气氛中焙烧制得氧化铝载体,然后在该载体上浸渍Ⅷ和ⅥB族活性金属组分,或是将拟薄水铝石、炭黑粉以及含Ⅷ和ⅥB族活性金属组分的化合物混捏均匀,成型、干燥,在含氧气氛中焙烧制得加氢脱金属催化剂。该方法采用物理扩孔的办法,以炭黑粉为扩孔剂,能够有效的提高催化剂的大孔含量,但是由于炭黑粉颗粒大小范围差别较大,使得孔分布较弥散,同时也导致催化剂机械强度较差。
CN106622265A公开了一种加氢脱金属催化剂及其制备方法和应用,该催化剂是将活性金属组分负载在经过改性处理的载体上,其中改性处理的载体制备方法是将经过水热处理的载体重复地依次进行浸渍和干燥,并将最后一次得到的干燥产物进行焙烧,然后将Ⅷ和ⅥB族活性金属组分负载在经过改性处理的载体上。该方法采用化学扩孔的办法,以酸性助剂化合物为扩孔剂,能够起到一定的扩孔作用,但是在对载体进行改性处理的时候,会对载体骨架结构造成损伤,导致催化剂机械强度降低。
CN102847541A公开了一种煤焦油加氢脱金属催化剂及其制备方法,制备方法是将氧化铝载体用pH值低于3的有机酸溶液处理后,用硝酸铝溶液浸渍,经过干燥、焙烧得到改性氧化铝载体,再将加氢活性组分负载在上述改性氧化铝上制得。该方法也是采用化学扩孔的办法来增大催化剂孔容积,通过酸处理再用硝酸铝浸渍酸处理后的氧化铝载体,可以克服上述CN106622265A的不足之处,但是该方法在载体改性过程步骤繁琐,且会产生二次污染。
发明内容:
本发明的目的就是针对上述现有技术的不足,提供一种催化剂孔占比大,孔分布集中,机械强度高,活性及稳定性好的煤焦油加氢脱金属催化剂;
本发明的另一目的就是提供一种制备工艺简单,不产生二次污染煤焦油加氢脱金属催化剂的制备方法。
本发明的目的是通过一下技术方案实现的:
煤焦油加氢脱金属催化剂,主要由氧化铝载体和加氢活性组分组成,该催化剂外形为三叶草,直径1.6~1.8mm,孔容﹥0.6ml/g,比表面﹥200m2/g,压碎强度﹥150N/cm,孔直径15~60纳米的孔占总孔的80%~95%;
所述的催化剂组成按重量百分比为:
氧化铝载体:85%~95%,
MoO3:2%~8%,
NiO:2%~5%,
P2O5:1%~2%。
所述的氧化铝载体制备过程中的物料按干基质量百分比配比如下:
氢氧化铝干胶粉:73%~91%
润滑剂:2%~6%
扩孔剂:5%~15%
烧结剂:2%~6%
水:100%~150%
所述的润滑剂为田菁粉、淀粉、甲基纤维素中的一种或多种,扩孔剂为草酸铵或者尿素,烧结剂为高岭土或凹凸棒石。
煤焦油加氢脱金属催化剂载体的制备方法,包括以下步骤:
A、按比例称取氢氧化铝干胶粉73%~91%、润滑剂2%~6%、扩孔剂5%~15%和烧结剂2%~6%,加水100%~150%混捏均匀后挤条成型;
B、采用冷冻干燥,通过冻结、升华和再干燥三个阶段,调节冷冻干燥过程中的温度和压力,控制水分分步释放,将载体中的表面水和结合水逐步去除,冻结温度-25℃~-35℃,冻结压力8pa~12pa;升华时控制冻干箱温度-
55℃~-65℃,冻干箱压力1pa~3pa,搁板温度10℃~30℃;再干燥温度25℃~35℃;
C、氧化铝载体制备焙烧,升温速度控制在20℃/h~25℃/h,温度500℃~600℃,焙烧时间3h~6h,获得氧化铝载体。
煤焦油加氢脱金属催化剂的制备方法,包括以下步骤:
a、按质量百分比MoO3:2%~8%,NiO:2%~5%和P2O5:1%~2%配制成加氢活性组分溶液;
b、采用等体积浸渍法,将配制的活性组分溶液负载在氧化铝载体上;
c、送干燥炉干燥,干燥温度100~150℃,干燥时间2~10h,
d、再经500~600℃焙烧,焙烧时间3~6h,制得煤焦油加氢脱金属催化剂。
有益效果:本发明制备的煤焦油加氢脱金属催化剂,在载体制备过程采用了冷冻干燥法,通过冻结、升华和再干燥3个阶段,调节过程中的温度和压力,控制水分的分步释放,将载体中的表面水和结合水逐步去除。冷冻干燥法能够有效避免传统的带式干燥或者箱式干燥存在的物料受热不均、前期干燥过快导致载体表面裂痕致使载体强度变差等问题,与其他干燥方法相比,干燥后的载体能够保持挤条成型后的原有框架结构,其组织结构和外观形态被较好地保存。干燥后的载体内部形成多孔的海绵状,为后续的焙烧扩孔过程提供便利条件。
在载体制备过程焙烧过程中,由于在前序过程中加入了扩孔剂、烧结剂、以及载体干燥后留下的多孔海绵状框架结构,在焙烧过程中,扩孔剂在高温下分解释放出气体,起到一定的扩孔作用,烧结剂的加入,在载体焙烧过程中将Si引入到Al-O键形成的网络中,打断了Al-O键间的联接,形成断网,降低了表面张力,孔壁塌陷导致孔径增大,调整烧结剂的加入量,能够直接有效的控制氧化铝载体的孔结构;
在载体制备过程焙烧过程中,由于烧结剂的加入使得烧结作用同时带来的有益效果是将氧化铝表面羟基缩合,降低载体的酸性,提高加氢脱金属催化剂反应稳定性。通过扩孔剂和烧结剂的双重作用,使得得到的氧化铝载体孔容大,孔分布集中,并且机械强度较高,具有适宜的表面酸性。
具体实施方式:
下面结合实施例对本发明做进一步的详细说明:
煤焦油加氢脱金属催化剂,主要由氧化铝载体和加氢活性组分组成,该催化剂外形为三叶草,直径1.6~1.8mm,孔容﹥0.6ml/g,比表面﹥200m2/g,压碎强度﹥150N/cm,孔直径15~60纳米的孔占总孔的80%~95%;
所述的催化剂组成按重量百分比为:
氧化铝载体:85%~95%,
MoO3:2%~8%,
NiO:2%~5%,
P2O5:1%~2%。
所述的氧化铝载体制备过程中的物料按干基质量百分比配比如下:
氢氧化铝干胶粉:73%~91%
润滑剂:2%~6%
扩孔剂:5%~15%
烧结剂:2%~6%
水:100%~150%
所述的润滑剂为田菁粉、淀粉、甲基纤维素中的一种或多种,扩孔剂为草酸铵或者尿素,烧结剂为高岭土或凹凸棒石。
煤焦油加氢脱金属催化剂载体的制备方法,包括以下步骤:
A、按比例称取氢氧化铝干胶粉73%~91%、润滑剂2%~6%、扩孔剂5%~15%和烧结剂2%~6%,加水100%~150%混捏均匀后挤条成型;
B、采用冷冻干燥,通过冻结、升华和再干燥三个阶段,调节冷冻干燥过程中的温度和压力,控制水分分步释放,将载体中的表面水和结合水逐步去除,冻结温度-25℃~-35℃,冻结压力8pa~12pa;升华时控制冻干箱温度-55℃~-65℃,冻干箱压力1pa~3pa,搁板温度10℃~30℃;再干燥温度25℃~35℃;
C、氧化铝载体制备焙烧,升温速度控制在20℃/h~25℃/h,温度500℃~600℃,焙烧时间3h~6h,获得氧化铝载体。
煤焦油加氢脱金属催化剂的制备方法,包括以下步骤:
a、按质量百分比MoO3:2%~8%,NiO:2%~5%和P2O5:1%~2%配制成加氢活性组分溶液;
b、采用等体积浸渍法,将配制的活性组分溶液负载在氧化铝载体上;
c、送干燥炉干燥,干燥温度100~150℃,干燥时间2~10h,
d、再经500~600℃焙烧,焙烧时间3~6h,制得煤焦油加氢脱金属催化剂。
实施例1:
①氧化铝载体制备。称取500g氢氧化铝干胶、7g田菁粉、7g草酸铵、18g高岭土,加入干混机中,干混均匀后缓慢将750g纯水加入,进行混捏碾压,碾压成可塑体后通过挤条机挤条成型,将成型的物料放入冷库冷却至2℃,然后置于-30℃压力10Pa冻干箱内将成型的物料快速冻结,将冻干箱内温度和压力降至-60℃压力2Pa,控制搁板温度10℃,待真空系统中由物料中的冰升华而来的水汽不再流出时,此时升高搁板至30℃进行物料的再干燥,排放真空系统中水汽冷凝器中的水,将物料中的结合水去除。干燥结束后控制升温速度25℃/h,在焙烧炉中控制温度520℃焙烧4h,制得氧化铝载体。
②催化剂制备。称取20g三氧化钼,25g碱式碳酸镍和22g磷酸,在搅拌下加入到350g纯水中,升温至沸腾搅拌0.5小时,制成浸渍溶液,通过喷浸装置将溶液均匀喷浸在上述氧化铝载体上,在流化床振动干燥机中控制温度100℃干燥8h,在520℃下焙烧4h,制得催化剂成品。
实施例2:
①氧化铝载体制备。称取500g氢氧化铝干胶、7g淀粉、7g尿素、18g凹凸棒石,加入干混机中,干混均匀后缓慢将750g纯水加入,进行混捏碾压,碾压成可塑体后通过挤条机挤条成型,将成型的物料放入冷库冷却至2℃,然后置于-30℃(10Pa)冻干箱内将成型的物料快速冻结,将冻干箱内温度和压力降至-60℃和2Pa,控制搁板温度10℃,待真空系统中由物料中的冰升华而来的水汽不再流出时,此时升高搁板至30℃进行物料的再干燥,排放真空系统中水汽冷凝器中的水,将物料中的结合水去除。干燥结束后控制升温速度20℃/h,在焙烧炉中控制温度520℃焙烧6h,制得氧化铝载体。
②催化剂制备。称取20g三氧化钼,25g碱式碳酸镍和22g磷酸,在搅拌下加入到350g纯水中,升温至沸腾搅拌0.5小时,制成浸渍溶液,通过喷浸装置将溶液均匀喷浸在上述氧化铝载体上,在流化床振动干燥机中控制温度100℃干燥8h,在520℃下焙烧4h,制得催化剂成品。
对比例1:
①氧化铝载体制备。称取500g氢氧化铝干胶、7g田菁粉、7g草酸铵、18g高岭土,加入干混机中,干混均匀后缓慢将750g纯水加入,进行混捏碾压,碾压成可塑体后通过挤条机挤条成型,将成型的物料放入箱式干燥箱,在120℃下干燥4h,干燥结束后控制升温速度25℃/h,在焙烧炉中控制温度520℃焙烧4h,制得氧化铝载体。
②催化剂制备。称取20g三氧化钼,25g碱式碳酸镍和22g磷酸,在搅拌下加入到350g纯水中,升温至沸腾搅拌0.5小时,制成浸渍溶液,通过喷浸装置将溶液均匀喷浸在上述氧化铝载体上,在流化床振动干燥机中控制温度100℃干燥8h,在520℃下焙烧4h,制得催化剂成品。
对比例2:
①氧化铝载体制备。称取500g氢氧化铝干胶,7g淀粉加入干混机中,干混均匀后缓慢将750g纯水加入,进行混捏碾压,碾压成可塑体后通过挤条机挤条成型,将成型的物料放入冷库冷却至2℃,然后置于-30℃(10Pa)冻干箱内将成型的物料快速冻结,将冻干箱内温度和压力降至-60℃和2Pa,控制搁板温度10℃,待真空系统中由物料中的冰升华而来的水汽不再流出时,此时升高搁板至30℃进行物料的再干燥,排放真空系统中水汽冷凝器中的水,将物料中的结合水去除。干燥结束后控制升温速度20℃/h,在焙烧炉中控制温度520℃焙烧6h,制得氧化铝载体。
②催化剂制备。称取20g三氧化钼,25g碱式碳酸镍和22g磷酸,在搅拌下加入到350g纯水中,升温至沸腾搅拌0.5小时,制成浸渍溶液,通过喷浸装置将溶液均匀喷浸在上述氧化铝载体上,在流化床振动干燥机中控制温度100℃干燥8h,在520℃下焙烧6h,制得催化剂成品。
上述实施例与对比例所得催化剂性质见表1:
表1催化剂物化性质
编号 | 实施例1 | 实施例2 | 对比例1 | 对比例2 |
孔容,ml/g | 0.57 | 0.58 | 0.52 | 0.48 |
比表面积,m2/g | 240 | 233 | 242 | 235 |
机械强度,N/cm | 226 | 225 | 190 | 205 |
MoO3,% | 5.1 | 5.2 | 5.1 | 5.2 |
NiO,% | 3.6 | 3.5 | 3.6 | 3.5 |
P2O5,% | 1.5 | 1.4 | 1.5 | 1.4 |
表1结果表明,本发明制得催化剂物化性质较对比例孔容和机械强度有所增加。
下面结合实例对上述实施例与对比例所得催化剂催化性能进行比较:
在200ml小型评价装置上对上述实施例与对比例所得催化剂进行评价试验,评价用煤焦油性质见表2,评价条件:温度330℃,压力12MPa,氢油比500,体积空速1.2h-1,反应300h后测定生成油性质,计算脱金属率及脱硫氮率,见表3。
表2煤焦油原料性质
项目 | 煤焦油原料 |
密度(20℃),kg/m-3 | 1020 |
硫,% | 0.12 |
氮,% | 1.0 |
氧,μg/g-1 | 3.5 |
残炭,% | 10 |
凝点,℃ | 10 |
含水,% | 4 |
馏程,℃ | 177~500 |
金属,μg/g-1 | 200 |
表3催化剂催化性能
编号 | 实施例1 | 实施例2 | 对比例1 | 对比例2 |
脱金属率,% | 85 | 84 | 65 | 62 |
脱硫率,% | 65 | 63 | 52 | 58 |
脱氮率,% | 46 | 42 | 35 | 38 |
由表3数据可以看出,由本方法制备的煤焦油加氢脱金属催化剂具有优异的脱金属及脱硫氮性能,工业应用表明,相对同类催化剂,该方法得到的加氢脱金属催化剂具有更高的活性及稳定性。
Claims (4)
1.一种煤焦油加氢脱金属催化剂,其特征在于,是由氧化铝载体和加氢活性组分组成,该催化剂外形为三叶草,直径1.6~1.8mm,孔容﹥0.6ml/g,比表面﹥200m2/g,压碎强度﹥150N/cm,孔直径15~60纳米的孔占总孔的80%~95%;
所述的催化剂组成按质量百分比为:
氧化铝载体:85%~95%,
MoO3:2%~8%,
NiO:2%~5%,
P2O5:1%~2%。
其中MoO3、NiO、P2O5为加氢活性组分
所述的氧化铝载体制备过程中的物料按质量百分比配比如下:
氢氧化铝干胶粉:73%~91%
润滑剂:2%~6%
扩孔剂:5%~15%
烧结剂:2%~6%
水:100%~150%
2.按权利要求1所述的煤焦油加氢脱金属催化剂,其特征在于,润滑剂为田菁粉、淀粉、甲基纤维素中的一种或多种,扩孔剂为草酸铵或尿素,烧结剂为高岭土或凹凸棒石。
3.按权利要求1所述的煤焦油加氢脱金属催化剂载体的制备方法,其特征在于,包括以下步骤:
A、按比例称取氢氧化铝干胶粉73%~91%、润滑剂2%~6%、扩孔剂5%~15%和烧结剂2%~6%,加水100%~150%混捏均匀后挤条成型;
B、采用冷冻干燥,经冻结、升华和再干燥三个阶段,调节冷冻干燥过程中的温度和压力,控制水分分步释放,将载体中的表面水和结合水逐步去除,冻结温度-25℃~-35℃,冻结压力8pa~12pa;升华时控制冻干箱温度-55℃~-65℃,冻干箱压力1pa~3pa,搁板温度10℃~30℃;再干燥温度25℃~35℃;
C、干燥后的氧化铝挤条再经500℃~600℃焙烧,控制升温速度在20℃/h~25℃/h,焙烧时间3h~6h,获得氧化铝载体。
4.按权利要求1所述的煤焦油加氢脱金属催化剂的制备方法,其特征在于,包括以下步骤:
a、按比例MoO3:2%~8%,NiO:2%~5%和P2O5:1%~2%配制成加氢活性组分溶液;
b、采用等体积浸渍法,将配制的活性组分溶液负载在氧化铝载体上;
c、送干燥炉干燥,干燥温度100~150℃,干燥时间2~10h,
d、再经500~600℃焙烧,焙烧时间3~6h,制得煤焦油加氢脱金属催化剂。
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