CN114618573B - 一种嵌入式Ni基催化剂、制备方法及应用 - Google Patents
一种嵌入式Ni基催化剂、制备方法及应用 Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 49
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract
本发明涉及一种嵌入式Ni基催化剂、制备方法及应用,属于催化剂制备领域。本发明制备的催化剂以NiO/SiO2为载体,同时作为活性金属前驱体和分子筛合成中的硅源,采用水热法原位合成了具有特殊嵌入式结构的Ni@Al‑MCF催化剂,其中Ni的质量百分含量为1~25wt%,Al的质量百分含量为1~10wt%。本发明制备的催化剂具有转化率高、稳定性好的优点,可以将有机过氧化物、醛类、酮类、酯类的含量降至10ppm以下,提高循环溶剂的纯度,延长丙烯环氧化催化剂的使用寿命。本发明催化剂原料易得,制备工艺简单,催化性能优异,适合工厂规模化生产。
Description
技术领域
本发明涉及催化剂制备领域,具体说是一种嵌入式Ni基催化剂、制备方法及应用。
背景技术
环氧丙烷(PO)是一种重要的有机合成原料,是除聚丙烯以外的第二大丙烯衍生物,其全球产能已超过1000万t/a。直接氧化法(HPPO法)是目前工业上相对成熟的环氧丙烷生产技术,具有工艺条件温和、产品选择性好、环境友好等特点,是目前公认的最具发展前景的绿色合成工艺。在HPPO工艺中,反应过程中存在大量的水、溶剂(比如甲醇)和过量的丙烯,除生成目的产物环氧丙烷外,还会生成醛类、酮类、酯类等杂质。这些杂质和未反应完的过氧化氢很难通过普通精馏的方式从溶剂中除去,从而影响环氧丙烷产品的品质及环氧化催化剂的使用寿命和选择性。因此,将有机过氧化物及醛类、酮类、酯类等杂质从溶剂除去是十分有必要的。
在HPPO反应液及环氧丙烷精制单元除杂质的方法有:专利CN100500659C通过添加包含未取代的-NH2与乙醛反应,专利CN102884055B使用胺官能化的离子交换树脂与乙醛反应,专利CN105906584B使用树脂吸附初级除醛,再使用乙醇胺或水合肼与醛反应,上述方法的缺点是引入了新的杂质及环氧丙烷损耗高,CN103119032B通过多级蒸馏的方法,投资高、运行成本高。在HPPO回收溶剂单元除杂质的方法有:采用传统载体加氢纯化溶剂,一般采用含贵金属元素的催化剂(如Ru、Pd等),但贵金属催化剂价格昂贵,不适合工业化大规模生产。镍基催化剂由于具有较高催化活性且与贵金属相比价格低廉,从而被广泛用于HPPO工艺回收溶剂纯化反应中。然而,镍基催化剂在反应过程中,由于碳沉积、金属颗粒烧结、镍流失和P杂质毒化等原因,常常导致反应出现失活现象。因此,开发一种高效的、抗积碳、抗烧结、抗镍流失和P杂质毒化等性能优异的Ni基催化剂用于除去HPPO工艺中杂质的方法是很有必要的。
发明内容
针对上述问题,本发明提供了一种嵌入式Ni基催化剂制备方法及应用,催化剂具有很高的除杂质效率,且稳定性能优异,具有很好的应用价值。
本发明的目的是提供一种嵌入式Ni基催化剂的制备方法,包括以下步骤:
(1)将可溶性Ni盐和去离子水混合配制成溶液A,将Si源加入到碱性溶液中配制成溶液B;
(2)在室温下,将溶液A用蠕动泵以3mL/min速率滴加至溶液B中,滴加过程不断搅拌,滴加完成后,用氢氧化钠溶液调PH至10,继续搅拌1~4h,抽滤,用去离子水洗涤滤饼至中性;
(3)取步骤(2)中洗涤后的滤饼在120℃下烘干,然后置于马弗炉中500℃下焙烧4h,即得NiO/SiO2载体;
(4)取三嵌段共聚物P123溶入去离子水后,在40℃的温度下搅拌至澄清,加入均三甲苯,继续搅拌4h,记为溶液C;
(5)将可溶性Al源和NiO/SiO2载体加入溶液C中,加氨水调PH至5.5-7.5,然后将上述溶液在40℃搅拌24h后,在100℃晶化48-72h,过滤,并用去离子水洗涤滤饼至滤液呈中性,将滤饼置于烘箱中,在120℃下干燥后,转移至马弗炉中于450-600℃煅烧4-8小时,得到所述嵌入式Ni基催化剂Ni@Al-MCF。
优选的,步骤(1)所述可溶性Ni盐为硝酸镍、氯化镍、硫酸镍、乙酸镍中的任意一种;所述溶液A中可溶性Ni盐的浓度为25~30g/L。
优选的,步骤(1)所述Si源为水玻璃、硅溶胶、气相SiO2、正硅酸乙酯;所述的碱性溶液为NaOH、尿素、Na2CO3或(NH4)2CO3中的一种或两种溶液的混合物,所述碱性溶液的浓度为30~40g/L;所述溶液B中Si源和碱性溶液的质量体积比为25g/100mL。
优选的,步骤(2)所述溶液A和溶液B的体积比为1~2:1~2。
优选的,步骤(2)所述溶液A的滴加速度为1~5mL/min。
优选的,步骤(4)所述P123和去离子水的质量体积比为2g/100mL;所述均三甲苯与P123的质量比为1~2:1~2。
优选的,步骤(5)所述可溶性铝源为硝酸铝、氯化铝、偏铝酸钠中的任意一种;所述可溶性铝源、NiO/SiO2载体和溶液C中P123的质量比为2~3:8~10:1~2。
本发明的另一目的是提供一种上述方法制备的催化剂,其特征在于:所述的催化剂中,Ni的含量为1~25wt%;Al2O3的含量为1~10wt%。
本发明制备的嵌入式Ni基催化剂可用于HPPO工艺回收溶剂纯化过程中,具体方法为:将所述催化剂置于10%H2/He的还原气氛中,在300~700℃的温度下原位还原1~6h,吹扫降温至70~90℃,反应压力升至1.0~3.0MPa,以体积空速4.0~10.0h-1回收溶剂,以体积空速0.06~0.1h-1通入氢气进行加氢反应。
与现有技术相比,本发明具有以下有益效果:
本发明以NiO/SiO2催化剂作为分子筛合成的硅源和铝源,经水热法成功合成出嵌入式结构Ni@Al-MCF催化剂,可以提高催化剂活性的同时,还可以有效抑制镍烧结,从而延长催化剂寿命。本发明的催化剂具有很高的除杂质效率,且稳定性能优异,具有很好的应用价值。
具体实施方式
实施例1
一种嵌入式Ni基催化剂的制备方法,步骤如下:
(1)将2.5g硝酸镍和100mL去离子水混合配制成溶液A;将25g水玻璃,加入100mL含有3.6g碳酸钠的去离子水中配制成溶液B;
(2)在室温下,将溶液A用蠕动泵以3mL/min速率滴加至溶液B中,滴加过程不断搅拌,滴加完成后,用2M的氢氧化钠溶液调PH至10,然后继续搅拌4h抽滤,并用去离子水洗涤滤饼至滤液呈中性;
(3)取步骤(2)中洗涤后的滤饼在120℃下烘干后,于马弗炉中500℃下焙烧4h,即得NiO/SiO2载体;
(4)称2g P123溶于100mL去离子水后,在40℃的温度下搅拌至澄清,加入2g均三甲苯,继续搅拌4h,记为溶液C;
(5)称取3.0g硝酸铝和8gNiO/SiO2载体,加入溶液C中,用1M氨水调PH至6.5,然后将上述溶液在40℃搅拌24h后,转入水热釜中100℃晶化72h,过滤,并用去离子水洗涤滤饼至滤液呈中性,取滤饼置于烘箱中,在120℃下烘干后,于马弗炉中550℃下焙烧6h,得到所述嵌入式Ni基催化剂Ni@Al-MCF。
本发明制备的催化剂中,Ni的质量百分含量为5.9wt%,Al的质量百分含量为2.6wt%。
对比例1
采用等体积浸渍法制备5wt%Ni/Al-MCF催化剂。具体过程如下:
(1)载体Al-MCF的制备:称取2gP123溶入60mLHCl(1.6M)中,40℃搅拌至澄清,加入2g均三甲苯,继续搅拌4h,记为溶液A;分别称取3.0g硝酸铝,25g水玻璃(SiO2质量含量29.8%)加入溶液A中,然后将上述溶液在40℃搅拌24h后,用浓氨水调PH至7.5,转入水热釜中100℃晶化48h;将悬浮液过滤,并用去离子水洗涤滤饼至滤液呈中性,取滤饼在120℃下烘干后,于马弗炉中550℃下焙烧6h,即制得Al-MCF载体。
(2)5wt%Ni/Al-MCF催化剂制备:将8.0gAl-MCF粉末加入到已配好的25mLNi(NO3)2·2H2O溶液中(含0.43gNi),在室温下静置12h后,转入60℃烘箱干燥12h。干燥后将试样在450℃空气气氛下煅烧4h。
以市售的负载镍催化剂为对照,对实施例1和对比例1制备的镍基催化剂的活性和寿命进行评价。催化剂活性测试是在固定床反应器上进行,反应压力为1.5MPa,实验过程如下:
将实施例1中得到的催化剂装入固定床反应器中,在大气压下向反应管内通入10%H2/He气体(20mL/min-1)于450℃下将催化剂原位还原4h后,吹扫降温至80℃,反应压力升至1.5MPa,以体积空速5.0h-1切换导入待纯化溶剂,以空速0.07h-1通入氢气进行加氢反应;反应完毕后检测回收溶剂中的过氧化氢、乙醛、丙醛、丙酮、甲酸甲酯、二甲氧基甲烷含量,实验结果见表1。
表1
由表1可以看出:嵌入法制得的Ni@Al-MCF催化剂,通过加氢反应,可以将回收溶剂中的过氧化氢、醛、酮、酯、二甲氧基甲烷含量将至10ppm以下,加氢效率明显高于市售、浸渍法制得的催化剂,且稳定性显著高于市售的工业催化剂。以上实验结果表明嵌入法优势显著,提高了加氢效率和稳定性能。
实施例2-4
制备方法同实施例1,不同之处在于步骤(1)所用的碱性溶液不同,如表2所示。对实施例2~4制备的催化剂进行环氧丙烷溶剂纯化实验评价,实验结果见表2。
表2
由表1和2可以看出:不同沉淀剂制得的催化剂,加氢效率顺序为Na2CO3≈尿素>(NH4)2CO3>Na2CO3和NaOH。
实施例5-7
制备方法同实施例1,不同之处在于所用的可溶性Ni盐不同,如表3所示。对实施例5~7制备的催化剂进行环氧丙烷溶剂纯化实验评价,实验结果见表3。
表3
由表1和3可以看出:不同可溶性Ni盐制得的催化剂,加氢效率顺序为硝酸镍≈乙酸镍>氯化镍>硫酸镍。
实施例8-9
制备方法同实施例1,不同之处在于所用的Si源不同,如表4所示。对实施例8和9制备的催化剂进行环氧丙烷溶剂纯化实验评价,实验结果见表4。
表4
由表1和4可以看出:不同硅源制得的催化剂,其加氢效率区别不大。
实施例10-11
制备方法同实施例1,不同之处在于所用的铝源不同,如表5所示。对其进行环氧丙烷溶剂纯化实验评价,实验结果见表5。
表5
由表1和5可以看出:不同铝源制得的催化剂,加氢效率顺序为硝酸铝>氯化镍>异丙醇铝。
本文中应用了具体个例对本发明实施方式进行了阐述,以上实施例的说明只是用于帮助理解本发明。应当指出,对于本技术领域的技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (8)
1.一种嵌入式Ni基催化剂的应用,其特征在于:将所述催化剂用于HPPO工艺回收溶剂纯化过程中,置于10%H2/He的还原气氛中,在300~700℃的温度下原位还原1~6 h,吹扫降温至70~90℃,反应压力升至1.0~3.0MPa,以体积空速4.0~10.0 h-1回收溶剂,以体积空速0.06~0.1h-1通入氢气进行加氢反应;
嵌入式Ni基催化剂的制备方法,包括以下步骤:
(1)将可溶性Ni盐和去离子水混合配制成溶液A,将Si源加入到碱性溶液中配制成溶液B;
(2)在室温下,将溶液A用蠕动泵以一定速率滴加至溶液B中,滴加过程不断搅拌,滴加完成后,用氢氧化钠溶液调PH至10,继续搅拌1~4h,抽滤,用去离子水洗涤滤饼至中性;
(3)取步骤(2)中洗涤后的滤饼在120℃下烘干,然后置于马弗炉中500℃下焙烧4h,即得NiO/SiO2载体;
(4)取三嵌段共聚物P123溶入去离子水后,在40℃的温度下搅拌至澄清,加入均三甲苯,继续搅拌4h,记为溶液C;
(5)将可溶性Al源和NiO/SiO2载体加入溶液C中,加氨水调PH至5.5-7.5,然后将上述溶液在40℃搅拌24h后,在100℃晶化48-72 h,过滤,并用去离子水洗涤滤饼至滤液呈中性,将滤饼置于烘箱中,在120℃下干燥后,转移至马弗炉中于450-600℃煅烧4-8小时,得到所述嵌入式Ni基催化剂Ni@ Al-MCF。
2.根据权利要求1所述嵌入式Ni基催化剂的应用,其特征在于:步骤(1)所述可溶性Ni盐为硝酸镍、氯化镍、硫酸镍、乙酸镍中的任意一种;所述溶液A中可溶性Ni盐的浓度为25~30g/L。
3.根据权利要求1所述嵌入式Ni基催化剂的应用,其特征在于:步骤(1)所述Si源为水玻璃、硅溶胶、气相SiO2、正硅酸乙酯;所述的碱性溶液为NaOH、尿素、Na2CO3或(NH4)2CO3中的一种或两种溶液的混合物,所述碱性溶液的浓度为30~40g/L;所述溶液B中Si源和碱性溶液的质量体积比为25g/100mL。
4.根据权利要求1所述嵌入式Ni基催化剂的应用,其特征在于:步骤(2)所述溶液A和溶液B的体积比为1~2:1~2。
5.根据权利要求1所述嵌入式Ni基催化剂的应用,其特征在于:步骤(2)所述溶液A的滴加速度为1~5mL/min。
6.根据权利要求1所述嵌入式Ni基催化剂的应用,其特征在于:步骤(4)所述P123和去离子水的质量体积比为2g/100mL;所述均三甲苯与P123的质量比为1~2:1~2。
7.根据权利要求1所述嵌入式Ni基催化剂的应用,其特征在于:步骤(5)所述可溶性铝源为硝酸铝、氯化铝、偏铝酸钠中的任意一种;所述可溶性铝源、NiO/SiO2载体和溶液C中P123的质量比为2~3:8~10:1~2。
8.根据权利要求1~7任意一项所述嵌入式Ni基催化剂的应用中采用的催化剂,其特征在于:所述的催化剂中,Ni的含量为1~25 wt%;Al2O3的含量为1~10 wt%。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003106168A1 (en) * | 2000-08-16 | 2003-12-24 | Lyotropic Therapeutics, Inc. | Coated particles, methods of making and using |
CN103100415A (zh) * | 2012-12-03 | 2013-05-15 | 北京化工大学 | 活性组分纳米颗粒嵌入分子筛结晶的催化剂、方法及应用 |
CN104888839A (zh) * | 2015-05-13 | 2015-09-09 | 北京化工大学 | 一种用于氨脱除的介孔分子筛基催化剂及其制备方法和应用 |
CN110871106A (zh) * | 2018-09-03 | 2020-03-10 | 北京化工大学 | 一种稳定运行的乙烷、丙烷转化催化剂的制备方法 |
CN111841591A (zh) * | 2020-06-29 | 2020-10-30 | 润泰化学(泰兴)有限公司 | 用于还原生物增塑剂新戊二醇二苯甲酸酯的Ni@MoC/NMC催化剂及制备方法 |
CN113731480A (zh) * | 2021-09-07 | 2021-12-03 | 中国科学院大连化学物理研究所 | 顺丁烯二酸酐加氢制γ-丁内酯反应催化剂及其制备和应用 |
-
2022
- 2022-04-01 CN CN202210347993.4A patent/CN114618573B/zh active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003106168A1 (en) * | 2000-08-16 | 2003-12-24 | Lyotropic Therapeutics, Inc. | Coated particles, methods of making and using |
CN103100415A (zh) * | 2012-12-03 | 2013-05-15 | 北京化工大学 | 活性组分纳米颗粒嵌入分子筛结晶的催化剂、方法及应用 |
CN104888839A (zh) * | 2015-05-13 | 2015-09-09 | 北京化工大学 | 一种用于氨脱除的介孔分子筛基催化剂及其制备方法和应用 |
CN110871106A (zh) * | 2018-09-03 | 2020-03-10 | 北京化工大学 | 一种稳定运行的乙烷、丙烷转化催化剂的制备方法 |
CN111841591A (zh) * | 2020-06-29 | 2020-10-30 | 润泰化学(泰兴)有限公司 | 用于还原生物增塑剂新戊二醇二苯甲酸酯的Ni@MoC/NMC催化剂及制备方法 |
CN113731480A (zh) * | 2021-09-07 | 2021-12-03 | 中国科学院大连化学物理研究所 | 顺丁烯二酸酐加氢制γ-丁内酯反应催化剂及其制备和应用 |
Non-Patent Citations (2)
Title |
---|
Identification of the structure of Ni active sites for ethylene oligomerization on an amorphous silica‐alumina supported nickel catalyst;Jinghua Xu et al.;Chinese Journal of Catalysis;第42卷(第12期);第2181-2188页 * |
Production of Biojet Fuel from Octadecane and Derivatives of Castor Oil Using a Bifunctional Catalyst Ni−Pd@Al-MCF in a Pressurized CO2−Hexane−Water Solvent;Saurav Bhattacharjee et al.;Energy Fuels;第36卷;第3119-3133页 * |
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