CN105727941B - 一种耐硫型芳烃饱和加氢催化剂及其制备方法 - Google Patents
一种耐硫型芳烃饱和加氢催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种耐硫型芳烃饱和加氢催化剂的制备方法,包括如下步骤:将贵金属与去离子水或酸溶液配成贵金属浸渍溶液,采用等体积浸渍法按照浸渍溶液浓度由高到低顺序浸渍到载体上,或配制高浓度的贵金属浸渍溶液逐步降低含有活性金属浸渍溶液的浓度的方式浸渍到载体上;经均化、干燥、焙烧后,得到耐硫型芳烃饱和加氢催化剂。本发明方法制备的芳烃饱和加氢催化剂主要用于处理低硫高芳烃轻质馏分油、中间馏分油、常压蜡油、减压蜡油。本发明方法的优点在于芳烃饱和加氢催化剂加氢精制性能好,芳烃饱和性能优异,产品液体收率高,同时脱硫性能和耐硫性能强,催化剂使用效果显著,应用前景广阔。
Description
技术领域
本发明涉及一种耐硫型芳烃饱和加氢催化剂的制备方法,尤其涉及处理低硫高芳烃轻质馏分油、中间馏分油、常压蜡油、减压蜡油的芳烃饱和加氢催化剂的制备方法。
背景技术
全球范围内,随着加工原油逐渐趋于重质化和劣质化,所加工的馏分油,现在已经达成共识,将柴油燃料中的芳烃化合物脱除可能有助于提高柴油十六烷值,脱除航空煤油原料中的芳烃化合物可有助于改善产品的烟点,脱除润滑油基础油原料中的芳烃可以改善产品的抗氧化安定性能。
相比非贵金属(钴、钼、镍、钨)硫化物催化剂,贵金属凸显出更加优异的加氢性能,所以贵金属催化剂广泛应用于馏分油原料的脱芳烃中。贵金属催化剂可以在较低温度下实现较好的脱除芳烃的性能。但是采用贵金属催化剂加工馏分油的加氢性能往往与它们对含硫化合物的敏感度有关,贵金属通常耐硫性能差,在加工馏分油的工艺过程中易造成贵金属催化剂中毒。然而有些炼厂的馏分油中含硫化合物含量较高,如果不预先对馏分油进行脱硫处理,直接采用贵金属催化剂进行脱芳烃是不合乎要求的。
专利US3943053公开了一种选择性的芳烃加氢催化剂,该专利称采用该方法制备的催化剂在很长一段时间加工含硫原料可以保持加氢性能,该方法中的催化剂采用高比表面积的γ-Al2O3为载体并负载铂和钯。催化剂制备的关键问题在于在相同水溶液中将铂和钯同时浸渍到载体上,没有对贵金属在催化剂上的分布状态进行介绍。
专利US5308814公开一种贵金属脱芳烃催化剂组合物的多种载体材料,专利中介绍以Y和耐高温无机氧化物(如二氧化硅、氧化铝、或二氧化硅和氧化铝)来制备载体,负载铂和钯,其中Y沸石在载体中比重为10~90%,因此可以推断该材料具有很强的裂化性,不适合用于加氢精制领域。
专利US4849093公开一种应用加氢处理催化剂两步脱芳烃饱和方法,该芳烃饱和催化剂包含非贵金属催化剂的第VIII族金属或第VIB金属或两者组合,专利并没有也没有对活性在催化剂上的分布状态进行介绍。
专利US3869522公开一种芳烃加氢方法,将含有10~90ω%二氧化硅、10~70ω%二氧化锆和0~25ω%氧化铝制成载体,专利优选铂作为活性金属,也可以与其它贵金属组合作为活性金属。对硫含量超标的原料可以进行催化脱硫。该专利认识到贵金属加氢催化剂暴露于含硫化物中会对含硫化物产生硫敏感,但是没有认识到通过改变贵金属在催化剂的分布状态来保护贵金属催化剂。
目前在工业中,通常都是配制含固定的活性金属浓度的浸渍溶液,通过饱和或过饱和浸渍到催化剂的载体上,再经过干燥、焙烧制成催化剂。美国专利US4399058介绍了一种加氢催化剂的制备方法,该专利中是将VIB族和VIII族金属盐与氨水混合,加氨水调节至某一pH值,制得固定浓度的活性金属溶液,再将金属溶液饱和浸渍到无机氧化物载体上,然后干燥和焙烧,得到加氢催化剂。
欧洲专利EP0204314介绍了一种不均匀活性金属组分分布的加氢催化剂制备方法,制备过程中采用分步,多次浸渍的方法负载活性金属组分,即先把活性组分A的溶液浸渍到载体上,再将载体经过水洗、干燥和焙烧,然后再浸渍含有活性组分B的浸渍液,载体再经过水洗干燥和焙烧。该专利采用分步水洗、干燥和焙烧的制备方法,使得催化剂中颗粒内部的活性金属含量高于其表面的金属含量,此种不均匀分布的催化剂与均匀分布的催化剂相比,催化剂的使用寿命延长了,但是该制备方法过于复杂,且制备过程中伴随着活性金属损失,造成催化剂制备成本偏高。
发明内容
本发明的目的在于提供一种耐硫型芳烃饱和加氢催化剂的制备方法,以期扩大芳烃饱和加氢原料的适应性,提升催化剂的耐硫性,使催化剂的使用寿命得到延长。本发明通过控制贵金属组分在催化剂颗粒内部梯度分布来提高贵金属的抗硫型能。
为实现上述目的,本发明提供了一种耐硫型芳烃饱和加氢催化剂的制备方法,包括如下步骤:
(1)将贵金属与去离子水或酸溶液配成贵金属浸渍溶液;
(2)采用等体积浸渍法将贵金属浸渍溶液浸渍到由无机多孔材料组成的载体上;
(3)均化10分钟~3小时,在90~140℃干燥3~6小时,在350~650℃下焙烧3~10小时,即得耐硫型芳烃饱和加氢催化剂;
所述步骤(2)中按照浸渍溶液浓度由高到低顺序浸渍到载体上,或配制高浓度的贵金属浸渍溶液,在浸渍过程中,逐步降低含有活性金属浸渍溶液的浓度。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述无机多孔材料优选由氧化铝和选自二氧化硅、二氧化钛-二氧化锆、氧化铝-二氧化硅、氧化铝-二氧化锆组成的群体中的至少一种组成。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述载体优选比表面积为150~500m2/g、孔容为0.2~0.7cm3/g。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述载体优选比表面积为200~400m2/g,孔容为0.3~0.6m3/g。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述无机多孔材料优选由氧化铝和选自二氧化硅、氧化铝-二氧化硅组成的群体中的至少一种组成时,铝和硅(以氧化铝和二氧化硅计)质量之比优选1:10~10:1;所述无机多孔材料优选由氧化铝和选自二氧化钛-二氧化锆、氧化铝-二氧化锆组成的群体中的至少一种组成时,铝和锆(以氧化铝和二氧化锆计)质量之比优选1:20~20:1。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述贵金属优选选自Pt、Pd、Ru、Rh、Re、Ir化合物组成的群体中的至少一种,催化剂中含有贵金属质量分数优选0.05~5.0ω%。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述贵金属优选Pt、Pd、Ru和Re化合物中的一种或两种,催化剂中含有贵金属质量分数优选0.2~2.0ω%。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述贵金属优选Pt和Pd,催化剂中含有Pt和Pd质量比优选1:6~6:1。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述酸溶液的酸组分优选选自盐酸、磷酸、磷酸氢盐、磷酸二氢盐、硫酸、硫酸一氢盐、醋酸、柠檬酸、硝酸组成的群体中的至少一种。
本发明所述的耐硫型芳烃饱和加氢催化剂的制备方法,其中所述催化剂的贵金属组分的浓度从颗粒中心到外表面梯度递减,以催化剂的颗粒横截面的外接圆圆心为起点,外接圆半径为R,在颗粒的外接圆圆心处与外接圆表面处贵金属含量比优选2.0~6.0,0.5R处与外表面处贵金属含量之比优选3.0~1.5。
在制备催化剂载体过程中,将无机多孔材料进行混捏,经过压片成型或挤条成型,催化剂形状为球形、圆柱形、三叶草形或四叶草形,经过干燥、高温焙烧制成载体。
本发明制备的芳烃饱和加氢催化剂优点在于贵金属活性组分在催化剂颗粒内部由中心到外部浓度呈梯度递减分布,催化剂芳烃饱和活性和稳定性优异,在处理低硫原料时耐硫性能强,催化剂兼具精制性能好,产品液体收率高的优点。本发明制备的芳烃饱和加氢催化剂在处理低硫高芳烃的轻质馏分油、中间馏分油、常压蜡油、减压蜡油具有显著效果,应用前景广阔。
附图说明
图1为实施例1、实施例3、对比例1和对比例2所制得的催化剂耐硫性和加氢脱硫性能的示意图。
图2为贵金属在催化剂中相对含量分布示意图。
图3为贵金属在催化剂中相对含量分布示意图。
具体实施方式
下面结合具体实施例对本发明作进一步的具体说明,但本发明不受下述实施例的限制。任何不超出本发明的构思和范畴的改动,都在本发明的范围之内。
实施例1:
以载体中含96ω%的Al2O3和Al2O3-SiO2与4ω%的ZrO2无机多孔材料机械混捏制成载体(载体中Al2O3与SiO2质量比为10:1,Al2O3与ZrO2质量之比为20:1),经过挤条、干燥、焙烧制成载体成品。
采用等体积浸渍方法制备催化剂载体,载体吸水率为0.89ml/g。称200g载体,喷浸78ml含1.0ω%的PtCl2、含0.3ω%的PdCl2的浸渍溶液,在喷浸过程中,将100ml含0.2ω%的PtCl2、含0.1ω%的PdCl2、含0.2mol/L酸浓度(H3PO4+HCl)的浸渍溶液匀速滴加到上述浸渍液中,30分钟滴加完毕。催化剂在喷浸设备中均化40分钟,在90℃干燥4小时,在550℃焙烧6小时,制得催化剂A-1。
实施例2:
以载体中含30ω%的Al2O3和SiO2、45ω%的ZrO2和25ω%的ZrO2-TiO2(载体中Al2O3与SiO2质量比为1:10,Al2O3与ZrO2质量之比为1:20)的无机多孔材料机械混捏制成载体,经过挤条、干燥、焙烧制成载体成品。
采用等体积浸渍方法制备催化剂载体,载体吸水率为0.89ml/g。称200g载体,喷浸78ml含1.0ω%的PtCl2、含0.3ω%的PdCl2的浸渍溶液,在喷浸过程中,将100ml含0.2ω%的PtCl2、含0.1ω%的PdCl2、含0.2mol/L酸浓度(硝酸+柠檬酸)的浸渍溶液匀速滴加到上述浸渍液中,30分钟滴加完毕。催化剂在喷浸设备中均化10分钟,在140℃干燥3小时,在500℃焙烧8小时,制得催化剂为A-2。
实施例3:
以载体中含60ω%的Al2O3和Al2O3-SiO2、20ω%的ZrO2和20ω%的ZrO2-TiO2无机多孔材料机械混捏制成载体(载体中Al2O3与SiO2质量比为5:1,Al2O3与ZrO2质量之比为5:1),经过挤条、干燥、焙烧制成载体成品。
采用等体积浸渍方法制备催化剂载体,载体吸水率为0.89ml/g。称200g载体,喷浸78ml含1.0ω%的PtCl2、含0.3ω%的PdCl2的浸渍溶液,在喷浸过程中,将100ml含0.2ω%的PtCl2、含0.1ω%的PdCl2、含0.2mol/L酸浓度(H3PO4+HCl)的浸渍溶液匀速滴加到上述浸渍液中,30分钟滴加完毕。催化剂在喷浸设备中均化3小时,在100℃干燥6小时,在650℃焙烧3小时,制得催化剂为A-3。
实施例4:
以载体中含45ω%的Al2O3-ZrO2、45ω%的Al2O3-SiO2和10ω%的TiO2无机多孔材料机械混捏制成载体(载体中Al2O3与SiO2质量比为1:1,Al2O3与ZrO2质量之比为1:1),经过挤条、干燥、焙烧制成载体成品。
采用等体积浸渍方法制备催化剂载体,载体吸水率为0.89ml/g。称200g载体,喷浸78ml含1.0ω%的PtCl2、含0.3ω%的PdCl2的浸渍溶液,在喷浸过程中,将100ml含0.2ω%的PtCl2、含0.1ω%的PdCl2、含0.3mol/L酸浓度(磷酸氢盐+磷酸二氢盐+醋酸)的浸渍溶液匀速滴加到上述浸渍液中,30分钟滴加完毕。催化剂在喷浸设备中均化50分钟,在90℃干燥5小时,在350℃焙烧10小时,制得催化剂为A-4。
实施例5:
以载体中含50ω%的Al2O3-SiO2、20ω%的Al2O3-ZrO2、10ω%的Al2O3和20ω%Al2O3-TiO2无机多孔材料机械混捏制成载体(载体中Al2O3与SiO2质量比为3:1,Al2O3与ZrO2质量之比为10:1),经过挤条、干燥、焙烧制成载体成品。
采用等体积浸渍方法制备催化剂载体,载体吸水率为0.89ml/g。其余均化、干燥和焙烧步骤与实施例1相同,不同在于浸渍步骤中酸溶液采用磷酸+硫酸+硫酸一氢盐混合溶液,浓度为0.25mol/L,制得催化剂为A-5。
实施例6:
与实施例1的区别在于,将喷浸100ml含1.0ω%的PtCl2、含0.3ω%的PdCl2的浸渍溶液,在喷浸过程中,将78ml含0.2ω%的PtCl2、含0.1ω%的PdCl2、含0.2mol/L酸浓度(H3PO4+HCl)的浸渍溶液匀速滴加到上述浸渍液中,其它步骤与实施例1相同,制得催化剂为A-6。
对比例1:
与实施例1的区别在于,以Al2O3原料制成载体,称取200g载体,采用等体积浸渍方法,喷浸178ml含0.55ω%的PtCl2、含0.19ω%的PdCl2和含0.11ω%酸浓度(H3PO4+HCl)为的浸渍溶液,其余步骤与实施例1相同,制得催化剂为B-1。
对比例2:
在制备催化剂过程中,与对比例1不同在于以SiO2为原料制成载体,制得催化剂为B-2。
实施例7:
采用EDS表征手段对催化剂A-1、A-2、A-3、A-4、A-5、A-6、B-1和B-2。
表1 催化剂物性结果
编号 | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | B-1 | B-2 |
Pt+Pd(中心)/Pt+Pd(外表) | 3.5 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 1.8 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 3.7 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 2.0 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 2.9 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 1.6 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 5.1 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 2.2 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 4.1 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 2.4 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 4.6 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 1.8 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 0.91 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 1.10 | |||||||
Pt+Pd(中心)/Pt+Pd(外表) | 0.94 | |||||||
Pt+Pd(0.5R)/Pt+Pd(外表) | 1.05 |
注:R为催化剂颗粒横截面的外接圆半径,以催化剂颗粒横截面的外接圆圆心为起点。
从表1可以看出,在实施例的A-1、A-2、A-3、A-4、A-5和A-6催化剂中,贵金属Pt和Pd,其含量从催化剂颗粒内部到外部都呈现出梯度递减的趋势,见图2或图3所示;而对比例的B-1和B-2催化剂中,贵金属Pt和Pd,在催化剂颗粒内部到外部分布相对都比较均匀。
实施例8:
以A-1、A-3、B-1和B-2为催化剂为例,进行真实原料加氢评价。
加氢评价反应在100ml加氢固定床上进行,评价原料油为加氢处理后的减压蜡油,原料性质如表2所示。
表2 原料油性质
密度(20℃),g/cm3 | 0.8629 |
馏程 | |
HK,℃ | 357 |
50%,℃ | 510 |
KK,℃ | 553 |
硫,μg/g | 63 |
芳烃含量,ω% | 31.4 |
评价工况条件如表3所示。
表3 评价工况条件
温度,℃ | 286 |
压力,MPa | 6.0 |
液时质量空速,h-1 | 0.75 |
氢油体积比 | 600 |
催化剂运转200小时后评价结果于表4,催化剂耐硫和加氢脱硫性能如图1。
表4 评价结果
从表4的评价结果看,本发明制备的芳烃饱和加氢催化剂精制性能好、芳烃饱和性能优异、液体收率高,优于传统方法制备活性组分均匀分布的加氢催化剂,同时从图1可以看出本发明制备的芳烃饱和加氢催化剂加氢脱硫性能和耐硫性能都表现较好,是潜在的芳烃饱和加氢催化剂。
Claims (11)
1.一种耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于,包括如下步骤:
(1)将贵金属与酸溶液配成贵金属浸渍溶液;
(2)采用等体积浸渍法将贵金属浸渍溶液浸渍到由无机多孔材料组成的载体上;
(3)均化10分钟~3小时,在90~140℃干燥3~6小时,在350~650℃下焙烧3~10小时,即得耐硫型芳烃饱和加氢催化剂;
其中,所述步骤(2)中的浸渍过程按照浸渍溶液浓度由高到低顺序浸渍到载体上。
2.根据权利要求1所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述步骤(2)中的浸渍过程为:配制高浓度的贵金属浸渍溶液,逐步降低含有活性金属浸渍溶液的浓度。
3.根据权利要求1所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述无机多孔材料由氧化铝和选自由二氧化硅、二氧化钛-二氧化锆、氧化铝-二氧化硅、氧化铝-二氧化锆组成的群组中的至少一种组成。
4.根据权利要求1所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述载体的比表面积为150~500m2/g、孔容为0.2~0.7cm3/g。
5.根据权利要求4所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述载体的比表面积为200~400m2/g、孔容为0.3~0.6m3/g。
6.根据权利要求3所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述无机多孔材料由氧化铝和选自二氧化硅、氧化铝-二氧化硅组成的群组中的至少一种组成时,铝和硅分别以氧化铝和二氧化硅计质量之比为1:10~10:1;所述无机多孔材料由氧化铝和选自二氧化钛-二氧化锆、氧化铝-二氧化锆组成的群组中的至少一种组成时,铝和锆分别以氧化铝和二氧化锆计质量之比为1:20~20:1。
7.根据权利要求1所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述贵金属选自由Pt、Pd、Ru、Rh、Re、Ir化合物组成的群组中的至少一种,催化剂中含有贵金属质量分数为0.05~5.0ω%。
8.根据权利要求7所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述贵金属为Pt、Pd、Ru和Re化合物中的一种或两种,催化剂中含有贵金属质量分数为0.2~2.0ω%。
9.根据权利要求7或8所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述贵金属为Pt和Pd,催化剂中含有Pt和Pd质量比为1:6~6:1。
10.根据权利要求1所述的耐硫型芳烃饱和加氢催化剂的制备方法,其特征在于所述酸溶液由酸性组分组成,所述酸性组分选自由盐酸、磷酸、磷酸氢盐、磷酸二氢盐、硫酸、硫酸一氢盐、醋酸、柠檬酸、硝酸组成的群组中的至少一种。
11.一种耐硫型芳烃饱和加氢催化剂,其是由权利要求1~9所述的耐硫型芳烃饱和加氢催化剂的制备方法制得的,其特征在于所述催化剂的贵金属组分的浓度从颗粒中心到外表面梯度递减,以催化剂的颗粒横截面的外接圆圆心为起点,外接圆半径为R,在颗粒的外接圆圆心处与外接圆表面处贵金属含量比为2.0~6.0,0.5R处与外表面处贵金属含量之比为3.0~1.5。
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CN113042021B (zh) * | 2019-12-27 | 2023-05-26 | 中国石油化工股份有限公司 | 一种沸腾床加氢催化剂及其制备方法 |
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