CN113649084B - 安全性多孔镍催化剂活性恢复的方法 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000000694 effects Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 18
- 239000012071 phase Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 17
- 229910000564 Raney nickel Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 3
- 238000005191 phase separation Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 12
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
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Abstract
本发明提供一种安全性多孔镍催化剂活性恢复的方法,以相剥离得到的安全性多孔镍催化剂,经干燥后,采用气相还原或/和液相清洗的方式,对其进行活性恢复,其性能与初始催化剂的性能相当。相比于传统的雷尼镍催化剂,操作安全,易于储存运输,活性恢复方法工艺简单,易于工业放大。
Description
技术领域
本发明属于新材料制备技术领域,涉及一种安全性多孔镍催化剂活性恢复的方法。
背景技术
工业雷尼镍(Raney Ni)催化剂,虽然活性高,应用广,但是易在空气中燃烧,因此需要液封保存,操作过程中存在安全隐患,且运输成本增加,因此开发安全性多孔镍催化剂至关重要。
申请人在专利CN202110310290.X公开了一种安全性多孔镍催化剂,该催化剂在众多反应中,均表现出明显优于传统雷尼镍的性能。然而此催化剂干燥后,其催化活性大大降低,因此需要开发一种能够恢复活性的方法。
工业雷尼镍催化剂为了便于储存,经常通过液相氧化处理后,进行干燥后储存。然而氧化剂的加入,导致氧化后催化剂的结构发生严重变化,通过还原后进行活性恢复,仅能恢复50%的活性。此外,雷尼镍的表面结构及组成与安全性多孔镍催化剂具有本质的区别,常见的活性恢复方法很难实现。
发明内容
本发明的目的是克服现有技术存在的上述问题,提供一种安全性多孔镍催化剂活性恢复的方法,设备简单,易于工业放大。
本发明的安全性多孔镍催化剂为具有多级孔结构的镍铝金属间化合物,所述镍铝金属间化合物中Ni/Al原子比为1:(3±0.5),所述催化剂的比表面积为50-100m2/g,多级孔中,一级孔的平均孔径为6-30nm,二级孔的平均孔径在5nm以下,一般为0.1-5nm。该催化剂经干燥后,活性大大降低,可以进行活性恢复以提高催化性能。
具体的,本发明的安全性多孔镍催化剂,以Ni、Al金属为原料,按照计量比制成复合合金,将复合合金破碎成粉末,采用选择性碱去除Al金属相,形成具有多级孔结构的金属间化合物粉末。原料中Ni/Al原子比为1:(9±4),破碎的粒度为200-400目,选择性碱采用碱金属族强碱,包括NaOH、KOH、Na2CO3中的一种或几种,浓度以氢氧根计为0.005M~1M,30℃以下处理10min-24h。
本发明上述安全性多孔镍催化剂经过干燥后,可以采用气相还原和/或液相清洗的方法对其进行活性恢复,当气相还原和液相清洗两种恢复方法先后配合使用时,活性恢复的催化剂在炔烃还原中表现出与初始催化剂基本相当的活性。其中,所述气相还原包括采用CO、H2或组合还原,还原温度为300℃~700℃,优选为350℃~500℃。
其中,所述液相清洗的方法为采用酸液清洗或碱液清洗,所述酸液为HCl、H2SO4的一种或几种,浓度为0.001M~0.1M,优选为0.001M~0.005M,所述碱液为NaOH、Na2CO3、KOH的一种或几种,浓度为0.001M~1M,优选为0.01M~0.015M。液相清洗的温度可以为常温操作,以不超过60℃为宜。
本发明安全性多孔镍催化剂干燥后的活性损失可能来源于多孔骨架表面的金属氧化,形成镍和铝的复合氧化物,例如NiOx(x≥1.5)和Al2O3-y(y<3),由于Al的掺杂形成的镍铝间复合合金有效保证了镍的安全稳定性,但在多孔骨架结构表面会形成相对更多的Al2O3-y(y<3)以及相对较少的NiOx(x≥1.5)。本发明采用气相还原,将分散在铝氧化物其中的镍氧化物首先进行还原,一方面防止Ni损失,另一方面能够同时利用铝氧化物对已还原的金属Ni进行保护,防止气相氛围结束后Ni的氧化出现反复,但同时也可能由于铝氧化物的客观存在提升了NiOx与气相反应的难度,气相还原处理的温度略高。铝氧化物由于具有两性,既能和酸反应,也能和碱反应,由于与碱反应能力较弱,需要适当提高碱浓度,但过高的碱浓度会腐蚀镍铝复合合金骨架中的Al,因此控制碱的浓度以0.01M左右为佳,酸液浓度需要维持在相对更低的水平,我们发现Al2O3-y(y<3)和镍铝复合合金骨架对酸更为敏感。第二步的液相清洗完成后可以直接对活性恢复后的安全性多孔镍催化剂产品进行液封保存,避免了二次干燥带来的活性损失问题。
相对于现有技术,本发明的有益效果如下:相比于传统的雷尼镍催化剂,操作安全,易于储存运输,催化剂活性可以完全得到恢复,活性恢复方法工艺简单,活性恢复率可达90%以上,易于工业放大。
具体实施方式
以下结合具体实施例,对本发明做进一步详述。在下文中,如无特殊说明,所述方法均为本领域常规方法,所使用得试剂均可通过商业途径购买获得。
实施例1
以不同镍与铝原料比例,经熔炼破碎成200-400目金属粉末(平均粒度50μm),最后经0.5M NaOH相剥离形成安全性多孔镍催化剂。将其直接应用苯乙炔常温常压加氢性能评价,反应性能如表1所示。
表1
实施例2
选用1号催化剂,经真空干燥后,进行不同条件的活性恢复实验,经恢复后,进行苯乙炔常温常压加氢性能评价,反应性能及活性恢复率如表2所示(干燥后,经实验,活性恢复前,苯乙炔的转化效率TOF为0.4h-1,苯乙烯选择性90.2%)。活性恢复率为经活性恢复处理后的反应性能数据(表2TOF)相对于直接应用的反应性能数据(表1TOF)的比例。
表2
实施例3
将以上制备的1号安全性多孔镍催化剂,应用于1,4-丁炔二醇的常温常压选择加氢反应中(1,4-丁炔二醇浓度为1wt%,水为溶剂,反应4h),其转化率为72.6%,1,4-丁烯二醇选择性为92.8%。若将其干燥后,在H2气氛下400℃还原与0.01M NaOH碱洗混合活化后,1,4-丁炔二醇的转化率可达71.1%,活性恢复率达98%。
实施例4
将以上制备的2号安全性多孔镍催化剂,应用于1,4-丁炔二醇的常温常压选择加氢反应中(1,4-丁炔二醇浓度为1wt%,水为溶剂,反应4h),其转化率为48.4%,1,4-丁烯二醇选择性为93.8%。若将其干燥后,在H2气氛下400℃还原与0.01M NaOH碱洗混合活化后,1,4-丁炔二醇的转化率可达47.1%,活性恢复率达97%。
实施例5
将以上制备的4号安全性多孔镍催化剂,应用于1,4-丁炔二醇的常温常压选择加氢反应中(1,4-丁炔二醇浓度为1wt%,水为溶剂,反应4h),其转化率为32.1%,1,4-丁烯二醇选择性为94.7%。若将其干燥后,在H2气氛下400℃还原与0.01M NaOH碱洗混合活化后,1,4-丁炔二醇的转化率可达31.0%,活性恢复率达96.5%。
实施例6
将以上制备的4号安全性多孔镍催化剂,应用于1,4-丁炔二醇的常温常压选择加氢反应中(1,4-丁炔二醇浓度为1wt%,水为溶剂,反应4h),其转化率为61.8%,1,4-丁烯二醇选择性为93.4%。若将其干燥后,在H2气氛下400℃还原与0.01M NaOH碱洗混合活化后,1,4-丁炔二醇的转化率可达60.3%,活性恢复率达97%。
以上所述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 (1)
1.一种安全性多孔镍催化剂活性恢复的方法,其特征在于,包括气相还原和液相清洗两个步骤:
所述气相还原包括CO还原,还原温度为300℃~700℃;
所述液相清洗为酸液清洗,所述酸液为HCl、H2SO4中至少一种,浓度为0.001M~0.1M;液相清洗的温度不超过60℃;
所述安全性多孔镍催化剂为具有多级孔结构的镍铝金属间化合物,Ni/Al原子比为1:(3±0.5),所述催化剂的比表面积为50-100m2/g,所述多级孔中一级孔的平均孔径为6-30nm,二级孔的平均孔径在5nm以下;
所述安全性多孔镍催化剂由下述方法获得:以Ni、Al金属为原料,按照Ni/Al原子比为1:(9±4)的计量比制成复合合金,将复合合金破碎成粒度为200-400目的粉末,采用选择性碱去除Al金属相,在30℃以下处理10min-24h,形成具有多级孔结构的金属间化合物粉末;所述选择性碱采用碱金属族强碱,包括NaOH、KOH、Na2CO3中的一种或几种,浓度以氢氧根计为0.005M~1M。
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