CN114950464A - 废油加氢催化剂及其制备方法和应用 - Google Patents
废油加氢催化剂及其制备方法和应用 Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 40
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- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
本发明涉及废油处理技术领域,提出了废油加氢催化剂及其制备方法和应用,所述废油加氢催化剂以纳米多孔γ‑Al2O3为载体,所述活性组分在所述载体中的负载量为25‑35%,所述纳米多孔γ‑Al2O3的孔径为50‑75nm,所述纳米多孔γ‑Al2O3的孔容为1.96‑2.15cm2/g,比表面积为350‑380cm3/g。通过上述技术方案,解决了现有技术中加氢催化剂在废油加氢过程中稳定性差、加氢效率低的问题。
Description
技术领域
本发明涉及废油处理技术领域,具体的,涉及废油加氢催化剂及其制备方法和应用。
背景技术
润滑油是用在各种类型汽车、机械设备上以减少摩擦,保护机械及加工件的液体或半固体润滑剂,在使用润滑油时会氧化、老化、恶化,混入金属粉末、燃料油组分以及添加剂等变成废润滑油,与新润滑油在质量指标上有明显差异。随着工业的迅速发展,废润滑油的量逐年增加,如何正确处置和回收利用废润滑油是当下亟需解决的问题。
传统的废润滑油再生方法有物理处理法和化学再生法,但是物理再生法仅适用于废油劣化程度较低的原料油,化学再生法则会在处理过程中产生大量无法处理的酸性物质,具有二次污染性。新型的废润滑油再生方法中加氢精制处理法由于再生油品质好、无污染被广泛使用。
废润滑油加氢精制工艺中常用的加氢催化剂有以Co-Mo、Ni-Mo、Ni-W、Co-W、Co-Mo-Ni、Ni-Mo-W等为活性组分,以氧化铝或硅溶胶为载体的加氢催化剂,这些加氢催化剂在废油加氢过程中存在着稳定性差、加氢效率低的问题。
发明内容
本发明提出废油加氢催化剂及其制备方法和应用,解决了相关技术中加氢催化剂在废油加氢过程中稳定性差、加氢效率低的问题。
本发明的技术方案如下:
本发明提出了一种废油加氢催化剂,以Ni-Mo-W为活性组分,以纳米多孔γ-Al2O3为载体,所述活性组分在所述载体中的负载量为25-35%,所述纳米多孔γ-Al2O3的孔径为50-75nm。
作为进一步的技术方案,所述纳米多孔γ-Al2O3的孔容为1.96-2.15cm2/g,比表面积为350-380cm3/g。
作为进一步的技术方案,所述纳米多孔γ-Al2O3由以下方法制备:将三氯化铝和聚乙二醇、聚乙烯吡咯烷酮加入到水和乙醇的混合溶液中,搅拌溶解后加入环氧丙烷,搅拌得到溶胶,在40℃老化后过滤、洗涤、干燥、焙烧,得到纳米多孔γ-Al2O3。
作为进一步的技术方案,所述聚乙二醇与聚乙烯吡咯烷酮的质量比为2:1。
作为进一步的技术方案,所述焙烧分为一次焙烧和二次焙烧,所示一次焙烧温度为550-600℃,时间为2-3h,二次焙烧温度为500-550℃,时间为1-2h,所述二次焙烧温度低于所述一次焙烧温度。
本发明中,纳米多孔γ-Al2O3制备时,采用两次焙烧,且二次焙烧温度小于一次焙烧温度,进一步促进了纳米多孔γ-Al2O3载体孔径分步的均匀性,从而进一步提高了纳米多孔γ-Al2O3的孔容和比表面积。
作为进一步的技术方案,所述活性组分中Ni、Mo、W的质量比为(4-5):(16-25):5。
本发明还提出了所述废油加氢催化剂的制备方法,包括以下步骤:将镍盐加入到氨水和乙二胺的混合溶剂中,溶解后,加入钨盐和钼盐,溶解得到浸渍液,浸渍载体后陈化、干燥、焙烧得到废油加氢催化剂。
作为进一步的技术方案,所述浸渍载体后陈化12-24h,在80-100℃干燥3-5h,在500-550℃焙烧3-5h,得到废油加氢催化剂。
本发明还提出了所述废油加氢催化剂的应用,所述废油加氢催化剂用于废油加氢催化生产生物柴油中。
本发明的工作原理及有益效果为:
1、本发明中,采用孔径为50-75nm、孔容为1.96-2.15cm2/g,比表面积为350-380cm3/g的纳米多孔γ-Al2O3为载体,负载Ni-Mo-W活性组分,得到的废油加氢催化剂的稳定性更强,抗积碳性能更好,且具有较高的催化活性,加氢效率高,有效解决了加氢催化剂在废油加氢过程中稳定性差、加氢效率低的问题。
2、本发明中,加氢催化剂载体纳米多孔γ-Al2O3制备时,以聚乙二醇与聚乙烯吡咯烷酮质量比为2:1的混合物作为模板剂,使得制备的载体在具有高的比表面积的同时孔径和孔容更大,负载催化剂活性组分后的加氢效率更高。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都涉及本发明保护的范围。
下述实施例及对比例中,聚乙二醇为PEG2000,聚乙烯吡咯烷酮为PVP k90。
实施例1
废油加氢催化剂,由以下方法制备:
(1)将24.14g三氯化铝和6g聚乙二醇、3g聚乙烯吡咯烷酮加入到90mL水和10mL乙醇的混合溶液中,搅拌溶解后加入100g环氧丙烷,搅拌得到溶胶,在40℃静置老化24h后过滤,滤饼用去离子水洗涤后在100℃下干燥5h,然后先在550℃焙烧3h再在500℃下焙烧2h,得到纳米多孔γ-Al2O3,孔容为2.03cm2/g,平均孔径为68.32nm,比表面积为358.13cm3/g;
(2)将0.24g将醋酸镍加入到9mL氨水和1mL三乙醇胺的混合溶剂中,溶解后,加入0.66偏钨酸铵和2.18g钼酸胺,溶解得到浸渍液,浸渍于10g纳米多孔γ-Al2O3载体后,陈化12h,在80℃干燥5h,在500℃焙烧5h,得到废油加氢催化剂。
实施例2
废油加氢催化剂,由以下方法制备:
(1)将24.14g三氯化铝和6g聚乙二醇、3g聚乙烯吡咯烷酮加入到90mL水和10mL乙醇的混合溶液中,搅拌溶解后加入100g环氧丙烷,搅拌得到溶胶,在40℃静置老化24h后过滤,滤饼用去离子水洗涤后在100℃下干燥5h,然后先在600℃焙烧2h再在550℃下焙烧1h,得到纳米多孔γ-Al2O3,孔容为2.14cm2/g,平均孔径为73.16nm,比表面积为352.46cm3/g;
(2)将0.24g将醋酸镍加入到9mL氨水和1mL三乙醇胺的混合溶剂中,溶解后,加入0.66偏钨酸铵和2.18g钼酸胺,溶解得到浸渍液,浸渍于10g纳米多孔γ-Al2O3载体后,陈化12h,在80℃干燥5h,在500℃焙烧5h,得到废油加氢催化剂。
实施例3
废油加氢催化剂,由以下方法制备:
(1)将24.14g三氯化铝和5.6g聚乙二醇、2.8g聚乙烯吡咯烷酮加入到90mL水和10mL乙醇的混合溶液中,搅拌溶解后加入100g环氧丙烷,搅拌得到溶胶,在40℃静置老化24h后过滤,滤饼用去离子水洗涤后在100℃下干燥5h,然后先在550℃焙烧3h再在500℃下焙烧2h,得到纳米多孔γ-Al2O3,孔容为1.96cm2/g,平均孔径为51.74nm,比表面积为376.62cm3/g;
(2)将0.24g将醋酸镍加入到9mL氨水和1mL三乙醇胺的混合溶剂中,溶解后,加入0.66偏钨酸铵和2.18g钼酸胺,溶解得到浸渍液,浸渍于10g纳米多孔γ-Al2O3载体后,陈化12h,在80℃干燥5h,在500℃焙烧5h,得到废油加氢催化剂。
实施例4
废油加氢催化剂,由以下方法制备:
(1)将24.14g三氯化铝和6g聚乙二醇、3g聚乙烯吡咯烷酮加入到90mL水和10mL乙醇的混合溶液中,搅拌溶解后加入100g环氧丙烷,搅拌得到溶胶,在40℃静置老化24h后过滤,滤饼用去离子水洗涤后在100℃下干燥5h,然后先在550℃焙烧3h再在500℃下焙烧2h,得到纳米多孔γ-Al2O3,孔容为2.03cm2/g,平均孔径为68.32nm,比表面积为358.13cm3/g;
(2)将1.18g将醋酸镍加入到10mL氨水和1mL三乙醇胺的混合溶剂中,溶解后,加入0.66偏钨酸铵和3.40g钼酸胺,溶解得到浸渍液,浸渍于10g纳米多孔γ-Al2O3载体后,陈化24h,在100℃干燥3h,在550℃焙烧3h,得到废油加氢催化剂。
对比例1
与实施例1的区别仅在于:
步骤(1)中用等量的聚乙二醇替换聚乙烯吡咯烷酮,得到纳米多孔γ-Al2O3,孔容为1.86cm2/g,平均孔径为51.29nm,比表面积为334.63cm3/g。
对比例2
与实施例1的区别仅在于:
步骤(1)中干燥后直接在550℃下焙烧5h,得到纳米多孔γ-Al2O3,孔容为1.93cm2/g,平均孔径为56.53nm,比表面积为349.73cm3/g。
对比例3
与实施例1的区别仅在于:
步骤(1)中干燥后先在500℃焙烧3h再在550℃下焙烧2h,得到纳米多孔γ-Al2O3,孔容为1.61cm2/g,平均孔径为48.31nm,比表面积为320.85cm3/g。
对实施例1、对比例1-3的废油加氢催化剂进行如下1000小时加氢评价:
废油原料:废润滑油经减压蒸馏得到,黏度指数为89,凝固点为-16℃,硫含量为295μg/g;
实验装置:100mL绝热床加氢反应装置;
实验条件:反应压力为6Mpa,入口温度300℃,废油原料体积空速2.0h-1,氢与油体积比300:1;
实验检测:每6小时取样分析产品硫含量;催化剂运转1000小时后采用元素分析仪测定催化剂中碳元素的含量;
检测结果见下表:
从上表中可以看出,与对比例1-3相比,实施例1的加氢催化剂具有更优的加氢脱硫活性、加氢稳定性和抗积碳性能。
以上仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.废油加氢催化剂,其特征在于,以Ni-Mo-W为活性组分,以纳米多孔γ-Al2O3为载体,所述活性组分在所述载体中的负载量为25-35%,所述纳米多孔γ-Al2O3的孔径为50-75nm。
2.根据权利要求1所述的废油加氢催化剂,其特征在于,所述纳米多孔γ-Al2O3的孔容为1.96-2.15cm2/g,比表面积为350-380cm3/g。
3.根据权利要求1所述的废油加氢催化剂,其特征在于,所述纳米多孔γ-Al2O3由以下方法制备:将三氯化铝和聚乙二醇、聚乙烯吡咯烷酮加入到水和乙醇的混合溶液中,搅拌溶解后加入环氧丙烷,搅拌得到溶胶,在40℃老化后过滤、洗涤、干燥、焙烧,得到纳米多孔γ-Al2O3。
4.根据权利要求3所述的废油加氢催化剂,其特征在于,所述聚乙二醇与聚乙烯吡咯烷酮的质量比为2:1。
5.根据权利要求3所述的废油加氢催化剂,其特征在于,所述焙烧分为一次焙烧和二次焙烧,所示一次焙烧温度为550-600℃,时间为2-3h,二次焙烧温度为500-550℃,时间为1-2h,所述二次焙烧温度低于所述一次焙烧温度。
6.根据权利要求1所述的废油加氢催化剂,其特征在于,所述活性组分中Ni、Mo、W的质量比为(4-5):(16-25):5。
7.如权利要求1-6任意一项所述废油加氢催化剂的制备方法,其特征在于,包括以下步骤:将镍盐加入到氨水和乙二胺的混合溶剂中,溶解后,加入钨盐和钼盐,溶解得到浸渍液,浸渍载体后陈化、干燥、焙烧得到废油加氢催化剂。
8.根据权利要求7所述的制备方法,其特征在于,所述浸渍载体后陈化12-24h,在80-100℃干燥3-5h,在500-550℃焙烧3-5h,得到废油加氢催化剂。
9.如权利要求1-6任意一项所述废油加氢催化剂或权利要求7-8任意一项所述制备方法制得的废油加氢催化剂的应用,其特征在于,所述废油加氢催化剂用于废油加氢催化生产生物柴油中。
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