CN101423775B - 一种选择性镍系加氢催化剂及其制备方法 - Google Patents

一种选择性镍系加氢催化剂及其制备方法 Download PDF

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CN101423775B
CN101423775B CN200710176670A CN200710176670A CN101423775B CN 101423775 B CN101423775 B CN 101423775B CN 200710176670 A CN200710176670 A CN 200710176670A CN 200710176670 A CN200710176670 A CN 200710176670A CN 101423775 B CN101423775 B CN 101423775B
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roastings
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CN101423775A (zh
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梁顺琴
钱颖
吕龙刚
孙利民
郑云弟
王廷海
吴杰
曹凤霞
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Petrochina Co Ltd
Petrochina Petrochemical Research Institute
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China Petroleum and Natural Gas Co Ltd
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Priority to MYPI2010001734A priority patent/MY150048A/en
Priority to JP2010532405A priority patent/JP5357170B2/ja
Priority to US12/741,017 priority patent/US20100298129A1/en
Priority to GB201008986A priority patent/GB2467086B8/en
Priority to KR1020107008005A priority patent/KR101469303B1/ko
Priority to PCT/CN2008/001781 priority patent/WO2009062386A1/zh
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Abstract

本发明涉及一种选择性镍系加氢催化剂及其制备方法，以氧化铝为载体，其特征在于以催化剂重量为100％计，含有活性组分14～20％氧化镍、2～8％氧化镧和/或氧化铈和1～8％VIB氧化物助剂，2～8％二氧化硅，1～8％碱土金属氧化物，催化剂比表面60～150m2/g，孔容0.4～0.6ml/g。该催化剂具有良好的加氢性能，尤其具有抗杂质及抗胶质的能力，并具有良好的加氢稳定性能，特别适用于中低馏分油双烯选择性加氢，尤其适用于全馏***解汽油双烯烃选择性加氢。

Description

一种选择性镍系加氢催化剂及其制备方法
技术领域
本发明涉及一种选择性镍系加氢催化剂及其制备方法，该催化剂适用于中低馏分油选择加氢，特别适用于裂解汽油馏分一段选择性加氢工艺。
背景技术
裂解汽油为乙烯裂解的副产品，约占乙烯生产能力的50％以上，其中含有高度不饱和烃，如：双烯烃、苯乙烯等，经过选择性加氢使之变成相应的单烯烃。随着我国乙烯生产能力的持续增强，裂解汽油加氢已向镍系催化剂方向进行全馏分加氢发展。国内裂解汽油原料的多变性、裂解装置及裂解方式的差异，使得部分厂家裂解汽油原料恶化、加氢负荷提高，杂质含量如砷等增加，进而使一段加氢钯系催化剂运行不佳。贵金属催化剂因杂质砷易于占据Pd的空轨道，且Pd含量仅为千分之几，位于催化剂表层，其抗砷、抗胶质能力差，抗水能力也不佳。非贵金属催化剂因结构差异和金属含量高等因素具有一定的容砷、抗胶质能力和耐水能力，其价格优势也比较显著。因此，开发新型镍系全馏***解汽油一段加氢催化剂是市场和技术竞争的需求。
US3472763报道了一种Ni/Al2O3双烯选择性加氢催化剂，活性组分Ni含量1～20％，助剂MoO3含量1～5％，助剂碱金属和碱土金属含量1～5％，催化剂孔容大于0.4ml/g，比表面大于30m2/g，此催化剂是由活性组分及助剂的水溶液浸渍Al2O3载体制得。CN1218822A报道了一种Ni/Al2O3适用于裂解汽油馏分的选择性加氢催化剂，该催化剂是将镍负载与含锂或碱土金属的氧化铝载体上制得的，此催化剂在承受加氢负荷及加氢稳定性方面欠佳。
一种优良的选择性加氢催化剂不仅要有较高的加氢活性，较好的选择性，更重要的是具有良好的稳定性，也就是说，催化剂要有抗杂质及抗胶质的能力，这样才能使催化剂寿命延长。
发明内容
本发明目的在于开发一种Ni系Al2O3负载型双烯选择性加氢催化剂，催化剂具有良好的加氢性能，尤其具有良好的加氢稳定性能，适用于全馏***解汽油选择性加氢。
本发明的选择性镍系加氢催化剂，以氧化铝为载体，其特征在于以催化剂重量为100％计，含有14～20％氧化镍、1～8％氧化镧和/或氧化铈和1～8％VIB氧化物助剂，2～8％二氧化硅，1～8％碱土金属氧化物，催化剂比表面60～150m2/g，孔容0.4～0.6ml/g。该催化剂特别适用于中低馏分油双烯选择性加氢，尤其适用于全馏***解汽油双烯烃选择性加氢。
本发明还提供一种该催化剂的制备方法，先将二氧化硅或其前驱物、碱土金属氧化物或其前驱物加入氧化铝载体中，在800～1100℃下焙烧3～6小时形成改性氧化铝载体；将活性组分镍及镧和/或铈、VIB元素的可溶性盐加入水中，充分溶解后，将溶液PH值调节到4～5形成浸渍液，浸渍改性氧化铝载体，浸渍后，在40～120℃烘干，350～450℃焙烧3～6小时，得到成品催化剂.
本发明还特别推荐一种改性氧化铝载体的制备过程为：在氧化铝水合物(拟薄水铝石)中加入硅溶胶、硝酸、水进行捏合后，挤条成型，40～120℃烘干，300～600℃焙烧4～6小时，将碱土金属氧化物，加入水溶解后形成浸渍液，用于浸渍成型后的载体，浸渍后在40～120℃烘干，800～1100℃焙烧4～6小时，制得改性氧化铝载体，使载体物性数据符合要求。
在本发明中催化剂中含有2～8％的二氧化硅，可以增加催化剂特别是载体在高温焙烧过程中的稳定性能，二氧化硅含量最好为3～4％。氧化镍含量最好为15～19％。
催化剂中含有碱土金属，经高温焙烧可调节催化剂酸性，提高催化剂加氢反应过程中的抗胶质性能。碱土金属中最好使用镁和/或锶，碱土金属氧化物含量最好为2～5％。
镧和/或铈以硝酸盐的形式溶解在浸渍液中加入，以提高催化剂加氢活性及稳定性能，氧化镧和/或氧化铈含量最好为3～5％。
加入VIB元素提高催化剂的加氢活性及抵抗硫等杂质性能，最好是Cr、Mo、W中的一种或多种，VIB元素氧化物含量最好为3～6％。
将活性组分及助剂的溶液分两次浸渍与成品催化剂载体上，提高催化剂上活性组分的分散性，提高催化剂的活性及稳定性能。
上述制备过程中所述的活性组分镍、助剂镁、锶、镧、铈等化合物可以是硫酸盐、硝酸盐、卤化物等，优选各自的硝酸盐，因为硝酸盐易溶于水，以便充分溶解，溶液稳定。
催化剂制备的原料氧化铝水合物可以采用二氧化碳法、氨法、硝酸法等制备的氧化铝水合物，但优选硝酸法制备的氧化铝粉，催化剂加氢性能更好。
本发明的催化剂在使用之前，需在350～400℃用氢气还原5～6小时，还原时氢气与催化剂的体积比为(150∶1)～(500∶1)。
本发明的加氢催化剂适用于双烯类的不饱和烃的选择性加氢过程，特别适用于全馏***解汽油馏分一段选择性加氢工艺。
本发明的加氢催化剂，具有良好的加氢性能，尤其具有抗杂质及抗胶质的能力，并有良好的加氢稳定性能。
具体实施方式
原材料来源：
硝酸镍：西安化学试剂厂生产；
硝酸镁、硝酸锶：由上海胶体化工厂生产；
硝酸铈、硝酸镧：江苏宜兴扶风镇申生试剂厂；
氧化铝粉：兰化翔鑫助剂厂。
分析方法：
油品馏程：采用石油产品试验方法SYB-2110-60测定；
碘价：采用ICl法测定，以克碘/100克油表示；
双烯：采用苹果酸酐法测定，以克碘/100克油表示；
砷含量：采用DV-4300原子发射光谱仪测定；
硫含量：采用WK-2B微库仑仪测定；
胶质：采用石油产品试验方法SYB-2103-60测定。
实施例1、
将140ml水、5ml硝酸(含量60％)、16ml硅溶胶(含40％二氧化硅)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，560℃焙烧4小时。取焙烧过的载体100g，然后将26g硝酸镁溶入水中，浸渍与载体上，在空气中120℃烘干，1050℃焙烧4小时，制得改性Al2O3载体。
将10g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸铈2.1g、钼酸铵0.3g，调节PH值到4，然后浸渍于10g载体上，陈化12小时，120℃烘干，400℃焙烧4小时，制得催化剂。
对比例1
将140ml水、5ml硝酸(含量60％)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，560℃焙烧4小时，取焙烧过的载体100g，然后将16.7g硝酸镁、3g硝酸锶溶入水中，浸渍与载体上，在空气中120℃烘干，1050℃焙烧4小时，制得Al2O3载体。
将10g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸铈2.1g、钼酸铵0.3g，调节PH值到4，然后浸渍于10g载体上，陈化12小时，120℃烘干，400℃焙烧4小时，制得催化剂。
实施例2、
将140ml水、5ml硝酸(含量60％)、14ml硅溶胶(含40％二氧化硅)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，460℃焙烧4小时。取焙烧过的载体100g，然后将20g硝酸镁、3.5g硝酸锶溶入水中，浸渍与载体上，在空气中120℃烘干，1000℃焙烧4小时，制得Al2O3载体。
将8.6g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸镧1.5g、钨酸铵0.6g，调节PH值到4，然后浸渍于10g载体上，陈化12小时，120℃烘干，350℃焙烧4小时，制得催化剂。
对比例2、
将140ml水、5ml硝酸(含量60％)、14ml硅溶胶(含40％二氧化硅)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，1000℃焙烧4小时，制得Al2O3载体。
将8.6g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸镧1.5g、钨酸铵0.6g，调节PH值到4，然后浸渍于10g载体上，陈化12小时，120℃烘干，350℃焙烧4小时，制得催化剂。
实施例3、
将140ml水、5ml硝酸(含量60％)、9ml硅溶胶(含40％二氧化硅)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，460℃焙烧4小时，取焙烧过的载体100g，然后将15.5g硝酸镁溶入水中，浸渍与载体上，在空气中120℃烘干，1030℃焙烧4小时，制得Al2O3载体。
将7.9g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸铈0.63g、硝酸镧0.62g、钨酸铵0.5g，调节PH值到4，然后浸渍于10g载体上，陈化12小时，120℃烘干，400℃焙烧4小时，制得催化剂.
对比例3、
将140ml水加入300g拟薄水铝石氧化铝粉中，捏合挤条成型，在空气中120℃烘干，1030℃焙烧4小时，制得Al2O3载体。
将7.9g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入钼酸胺0.6g，调节PH值到4，然后浸渍于10g载体上，陈化12小时，120℃烘干，400℃焙烧4小时，制得催化剂。
实施例4、
将140ml水、5ml硝酸(含量60％)、12ml硅溶胶(含40％二氧化硅)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，460℃焙烧4小时，取焙烧过的载体100g，然后将5.8g硝酸锶溶入水中，浸渍与载体上，在空气中120℃烘干，1020℃焙烧4小时，制得Al2O3载体。
将9.5g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸铈1.1g、硝酸镧1.1g、铬酸钾0.6g，调节PH值到4，然后将浸渍液浸渍于10g载体上，陈化12小时，120℃烘干，350℃焙烧4小时，制得催化剂。
对比例4、
将140ml水、5ml硝酸(含量60％)、12ml硅溶胶(含40％二氧化硅)加入300g拟薄水铝石氧化铝粉中，捏合后挤条成型，在空气中120℃烘干，460℃焙烧4小时，取焙烧过的载体100g，然后将21.6g硝酸镁溶入水中，浸渍与载体上，在空气中120℃烘干，1020℃焙烧4小时，制得Al2O3载体。
将9.5g硝酸镍加入到20ml水中搅拌溶解，搅拌中加入硝酸铈1.1g，调节PH值到4，然后将浸渍液浸渍于10g载体上，陈化12小时，120℃烘干，350℃焙烧4小时，制得催化剂。
采用全馏***解汽油为原料，原料性质见表1，对实施例1、2、3、4及对比例1、2、3、4中的催化剂进行评价，催化剂评价是在100ml绝热床加氢反应装置上进行的，催化剂首先在350～400℃氢气下还原10小时，然后降温到60℃，用含二甲基二硫1000ppm的环己烷钝化2小时后进原料油。反应条件：反应压力：2.8MPa，入口温度：室温～60℃，新鲜原料油空速：3.5h-1，氢与油体积比：200∶1(体积比以新鲜油计)。分别评价200小时，每6小时取样分析产品碘价、双烯。每个催化剂在200小时评价中分析的产品碘价、双烯的平均数据见表2。
表1加氢原料油(C5～C9)指标
颜色   碘价×10<sup>-2</sup>(g/g)   双烯×10<sup>-2</sup>(g/g) 馏程(℃)   硫含量(ppm)   胶质×10<sup>-2</sup>(mg/ml) 密度(g/ml)   砷含量(ppb)
  黄色   89.2   38.5   45～205   96   6.0   0.815   ＜20
表2实施例及对比例催化剂组成及200小时评价平均数据
Figure G2007101766709D00071
将实施例2的催化剂样品进行1000小时长周期评价，催化剂评价是在100ml绝热床加氢反应装置上进行的，催化剂首先在400～450℃氢气下还原10小时，然后降温到60℃，用含二甲基二硫1000ppm的环己烷钝化3小时后进原料油。反应条件：反应压力：2.8MPa，入口温度：室温～70℃，新鲜原料油空速：2.8h-1，氢与油体积比：200∶1(体积比以新鲜油计)。每12小时取样分析产品碘价、双烯，取每隔200小时内的平均分析数据。加氢原料油(C5～C9)指标见表3。
表3加氢原料油(C5～C9)指标
颜色   碘价×10<sup>-2</sup>(g/g)   双烯×10<sup>-2</sup>(g/g) 馏程(℃)   硫含量(ppm)   胶质×10<sup>-2</sup>(mg/ml)   密度(g/ml)   砷含量(ppb)
  黄色   88.5   39.5   45～205   86   7   0.815   26
评价结果见表4。在投入原料的1000小时运转过程中，加氢产品的碘价和双烯值一直保持在较低的水平，这充分说明实施例2催化剂稳定性好，加氢活性良好。
表4、实施例2的催化剂样品与对比例3催化剂样品的1000小时评价数据

Claims (9)

1.一种选择性镍系加氢催化剂，以氧化铝为载体，其特征在于以催化剂重量为100％计，含有活性组分14～20％氧化镍，2～8％氧化镧和/或氧化铈，1～8％VIB氧化物助剂，2～8％二氧化硅，以及1～8％碱土金属氧化物，催化剂比表面积为60～150m2/g，孔容为0.4～0.6ml/g。
2.根据权利要求1所述的催化剂，其特征在于催化剂中氧化镍含量15～19％。
3.根据权利要求1所述的催化剂，其特征在于催化剂中氧化镧和/或氧化铈含量为3～5％。
4.根据权利要求1所述的催化剂，其特征在于所述碱土金属为镁和/或锶。
5.根据权利要求1所述的催化剂，其特征在于所述碱土金属氧化物含量为2～5％。
6.根据权利要求1所述的催化剂，其特征在于所述VIB元素选自铬、钼、钨中的一种或多种。
7.根据权利要求1所述的催化剂，其特征在于所述VIB元素氧化物含量为3～6％。
8.一种权利要求1所述催化剂的制备方法，其特征在于先将二氧化硅或其前驱物、碱土金属氧化物或其前驱物加入至氧化铝载体中，在800～1100℃下焙烧4～6小时形成改性氧化铝载体；将活性组分镍及稀土元素、VIB元素的可溶性盐加入水中，充分溶解后，将溶液pH值调节到4～5形成浸渍液，浸渍改性氧化铝载体，浸渍后，在40～120℃烘干，并在350～450℃焙烧4～6小时，得到成品催化剂。
9.根据权利要求8所述催化剂的制备方法，其特征在于所述改性氧化铝载体是通过下述方法获得：在氧化铝水合物中加入硅溶胶、硝酸、水进行捏合后，挤条成型，40～120℃烘干，300～600℃焙烧4～6小时，将硝酸镁或硝酸锶加入水溶解后，用于浸渍成型后的载体，40～120℃烘干，800～1100℃焙烧4～6小时，制得改性氧化铝载体。
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