CN111097419A - 一种甲烷化催化剂及其制备方法 - Google Patents
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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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
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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
- 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
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/76—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
- B01J23/78—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 alkali- or alkaline earth metals
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- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
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- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
- C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
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- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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Abstract
本发明涉及催化剂领域的一种甲烷化催化剂及其制备方法。所述甲烷化催化剂,以其重量为百分比计,包含以下组分:活性组分5~65wt%;载体35~95wt%;所述的活性组分选自Ni、Fe、Co中的至少一种。本发明将所述活性组分对应的可溶性盐配置成溶液A;将水溶性高分子配置成溶液B,将溶液A和B完全混合、搅拌均匀后浸渍到载体上,经干燥焙烧后可制得成品甲烷化催化剂。所述的甲烷化催化剂制备方法所制备的催化剂能够有效提高活性组分的分散度、增加催化剂的活性。
Description
技术领域
本发明涉及催化剂领域,更进一步说,涉及一种甲烷化催化剂及其制备方法。
背景技术
随着石油资源的日趋紧张,基于费托合成的煤炭转化技术吸引了能源巨头和学术界的重视。甲烷化作为费托合成中最简单的反应,主要应用于乙烯工业、合成氨、净化氢气和煤气化领域,旨在将COx转化为甲烷,或除去原料气中的杂质COx从而达到净化的目的。其中天然气是化石能源之一,主要应用于化工、燃料领域,其主要成分甲烷可由合成气(COx、H2)催化转化得到。作为最简单的费-托合成反应,甲烷化具有热值高、转化率高、产品单一和经济效益好等优点。
甲烷化的反应方程式如下:
CO+3H2→CH4+H2O ΔH0=-206KJ/mol
CO2+4H2→CH4+2H2O ΔH0=-165KJ/mol
目前市场上的甲烷化催化剂种类非常广泛,其组成基本由载体与活性组分构成。其中载体作为催化剂的重要组成部分,是主催化剂的分散剂、黏合物或支撑体,是负载主催化剂的骨架。载体的功能主要是提供有效的表面和适宜的孔结构,增强催化剂的机械强度,使催化剂具有一定的适应外界变化的能力,改善催化剂的热传导性和提供附加的活性中心等。催化剂的宏观结构,如比表面、孔结构、孔隙率和孔径分布等,对催化剂的活性和选择性会有很大的影响,而这种宏观结构又往往由载体来决定。为了适应工业上强放/吸热反应的需要,载体一般应具有较大的热容和良好的导热性,使反应热能迅速传递出/进去,避免局部过热而引起催化剂的烧结和失活或设备损坏,还可以避免高温下的副反应,从而提高催化剂的选择性。
对于CO甲烷化反应,具有高催化活性的活性组分是Ru、Ni、Fe、Co、Pd、Pt等。Fe基催化剂因原料价格低廉、来源丰富,成为工业催化剂设计的较佳选择。Co基催化剂对苛刻环境的耐受性相对较强。具有工业化应用前景的CO甲烷化催化剂主要是Ru基催化剂和Ni基催化剂,Ru基催化剂比Ni基催化剂的活性高,一度成为研究热点,但Ru作为贵金属,价格昂贵,且Ru与CO形成的Ru(CO)x络合物易升华造成活性组分流失。因此,近年来Ni基催化剂成为CO甲烷化催化剂的发展方向。Ni基催化剂上甲烷化反应活性较高,选择性好,且价廉易得,是最具工业应用前景的催化剂,国内的甲烷化催化剂主要为J系列,例如J103、J104、J105等。这些催化剂主要以Ni为活性组分,属于镍系活性组分,镍含量一般在10~40wt%之间。
高分子一般指相对分子质量高达几千到几百万的化合物,由于其自身性质突出,被广泛应用于尖端技术、工业引用以及居民生活中。高分子种类非常丰富,其中水溶性高分子是一种强亲水性的高分子材料,能溶解或溶胀于水中形成水溶液或分散体系。水溶性高分子按照亲水基团可分为阳离子型,阴离子型及非离子型水溶性高分子三类,阳离子基团,如叔胺基、季胺基等,阴离子基团,如羧酸基、磺酸基、磷酸基、硫酸基等,极性非离子基团,如羟基、醚基、胺基、酰胺基等。按照其来源可以分为天然水溶性高分子、半合成水溶性高分子和合成水溶性高分子,天然水溶性高分子以植物或动物为原料,通过物理或物理化学方法提取,主要有淀粉类、海藻类、植物胶和动物胶等,半合成水溶性高分子由天然物质经化学改性而得,主要有改性纤维素和改性淀粉,合成类水溶性高分子有聚合类和缩合类两大类。
发明内容
为了解决现有技术中存在的上述问题,本发明提出一种甲烷化催化剂。具体地说涉及一种甲烷化催化剂及其制备方法。
本发明目的之一是提供一种甲烷化催化剂,以其总重量为百分比计,可包含以下组分:
活性组分5~65wt%;优选10~60wt%;
载体35~95wt%;优选40~90wt%。
更优选地,包含以下组分:
活性组分30~60wt%;
载体40~70wt%。
其中,
所述的活性组分可选自Ni、Fe、Co中的至少一种。
所述的载体可选自氧化铝、氧化锆、稀土氧化物、氧化镁、氧化钡、水滑石、水泥、尖晶石、方镁石、二氧化钛、高岭土、硅藻土、二氧化硅、复合金属氧化物中的至少一种。
其中,所述的复合金属氧化物可选自Al2O3-SiO2、Al2O3-MgO、Al2O3-TiO2、Al2O3-ZrO2、SiO2-MgO、SiO2-TiO2、SiO2-ZrO2、MgO-TiO2、MgO-ZrO2、TiO2-ZrO2、Al2O3-SiO2-MgO、Al2O3-SiO2-TiO2、Al2O3-SiO2-ZrO2、SiO2-MgO-TiO2、SiO2-MgO-ZrO2、MgO-TiO2-ZrO2、Al2O3-SiO2-MgO-TiO2、Al2O3-SiO2-MgO-ZrO2、SiO2-MgO-TiO2-ZrO2、Al2O3-SiO2-MgO-TiO2-ZrO2中的至少一种。
所述的甲烷化催化剂,其特征在于是将包含所述活性组分对应的可溶性盐、水溶性高分子在内的组分浸渍到载体上经干燥焙烧后而制得。
本发明目的之二是提供一种甲烷化催化剂的制备方法,可包括以下步骤:
按所述用量将所述活性组分对应的可溶性盐配置成溶液A;将水溶性高分子配置成溶液B,将溶液A和B完全混合、搅拌均匀后浸渍到载体上,经干燥焙烧后可制得成品甲烷化催化剂。
其中,
配制溶液A、B的溶剂均为水,优选为去离子水;按最大溶解度进行溶解,溶剂的用量满足将活性组分对应的可溶性盐、水溶性高分子完全溶解即可。
具体操作中,溶液A中溶剂与活性组分对应的可溶性盐的重量用量可为1:(1~4),可根据实际情况进行调节,充分溶解即可。
活性组分对应的可溶性盐具体可选择本领域常见的水溶性盐,具体可选硝酸盐、碳酸盐等,优选硝酸盐。
所述浸渍方法可使用等体积浸渍法,具体可将溶液A、B加入到载体中即可。
所述水溶性高分子的用量可为还原后得到的催化剂成品中的所述活性组分和载体的总重量的0.1~10wt%。
所述的水溶性高分子可选自聚乙烯醇、聚丙烯酰胺、聚丙烯酸、聚氧乙烯、聚乙二醇(分子量200~20000)、聚马来酸酐、聚乙烯吡咯烷酮、羧甲基纤维素中的至少一种。
所述的干燥温度可为60~140℃,干燥时间为1~10h。
所述的焙烧温度可为250~650℃,焙烧时间为1~10h。
将活性组分相应的水溶液与水溶性高分子均匀混合在一起,同时负载于载体上。在浸渍的过程中,高分子对活性组分起到间隔作用,避免活性组分聚集、堆积进而遮盖活性中心,经过干燥焙烧后,间隔在活性组分的高分子在焙烧后完全分解为气体,仅剩下活性组分停留在载体表面,从而可以提高催化剂的活性组分的分散度,增加催化剂的活性。本发明的催化剂适用于乙烯工业的甲烷化反应,及煤气化或者化肥工业领域的甲烷化反应,优选乙烯工业的甲烷化反应。
本发明与现有技术相比具有以下优势:
本发明所述的甲烷化催化剂制备方法所制备的催化剂能够有效提高活性组分的分散度、增加催化剂的活性。
具体实施方式
下面结合实施例,进一步说明本发明。但本发明不受这些实施例的限制。
本申请实施例中原料均为市售。
实施例1
将10g硝酸镍(Ni(NO3)2.6H2O)溶于去离子水中搅拌均匀、1.2g聚丙烯酰胺溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g氧化铝(Al2O3)上,将浸渍后的产物置入80℃的烘箱中,干燥1h,将干燥后的产物置入马弗炉内在400℃下焙烧6h得到催化剂产品。
实施例2
将30g硝酸铁(Fe(NO3)3)溶于去离子水中搅拌均匀、0.5g聚丙烯酸溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g氧化镁(MgO)上,将浸渍后的产物置入60℃的烘箱中,干燥10h,将干燥后的产物置入马弗炉内在400℃下焙烧3h得到催化剂产品。
实施例3
将10g硝酸钴(Co(NO3)2.6H2O)溶于去离子水中搅拌均匀、0.7g聚乙二醇20000溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g氧化锆(ZrO2)上,将浸渍后的产物置入140℃的烘箱中,干燥1h,将干燥后的产物置入马弗炉内在500℃下焙烧1h得到催化剂产品。
实施例4
将35g硝酸镍(Ni(NO3)2.6H2O)溶于去离子水中搅拌均匀、0.2g羧甲基纤维素溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g氧化硅(SiO2)上,将浸渍后的产物置入120℃的烘箱中,干燥2h,将干燥后的产物置入马弗炉内在350℃下焙烧10h得到催化剂产品。
实施例5
将40g硝酸铁(Fe(NO3)3)溶于去离子水中搅拌均匀、0.9g聚乙烯醇溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g氧化钡(BaO)上,将浸渍后的产物置入100℃的烘箱中,干燥8h,将干燥后的产物置入马弗炉内在500℃下焙烧4h得到催化剂产品。
实施例6
将60g硝酸钴(Co(NO3)2.6H2O)溶于去离子水中搅拌均匀、0.4g聚乙烯吡咯烷酮溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g复合金属氧化物氧化铝-氧化钛(Al2O3–TiO2)上,将浸渍后的产物置入90℃的烘箱中,干燥6h,将干燥后的产物置入马弗炉内在400℃下焙烧2h得到催化剂产品。
实施例7
将20g硝酸镍(Ni(NO3)2.6H2O)溶于去离子水中搅拌均匀、1g聚丙烯酸溶于去离子水中搅拌均匀,将上述两种溶液混合后搅拌均匀使用等体积浸渍法浸渍负载于10g复合金属氧化物氧化铝-氧化镁(Al2O3–MgO)上,将浸渍后的产物置入80℃的烘箱中,干燥3h,将干燥后的产物置入马弗炉内在600℃下焙烧1h得到催化剂产品。
对比例1
将10g硝酸镍(Ni(NO3)2.6H2O)溶于去离子水中搅拌均匀、将上述溶液搅拌均匀使用等体积浸渍法浸渍负载于10g氧化铝(Al2O3)上,将浸渍后的产物置入80℃的烘箱中,干燥1h,将干燥后的产物置入马弗炉内在400℃下焙烧6h得到催化剂产品。
对比例2
将30g硝酸铁(Fe(NO3)3)溶于去离子水中搅拌均匀、将上述溶液搅拌均匀使用等体积浸渍法浸渍负载于10g氧化镁(MgO)上,将浸渍后的产物置入60℃的烘箱中,干燥10h,将干燥后的产物置入马弗炉内在400℃下焙烧3h得到催化剂产品。
甲烷化反应性能测试:
量取5mL催化剂装入不锈钢固定床反应器,通入高纯N2,流量为300mL/min,升温至120℃,将高纯N2切换为H2,流量为200mL/min升温至400~450℃并保持4h,然后将H2切换为原料气,在150~250℃不同反应温度下,切入原料气,反应压力为3.0MPa,反应后气体组成使用安捷伦7890气相色谱分析。(原料气组成:CO0.5%;CO20.05%;H2 99.45%)
按照上述评价方法,对实施例1~7和对比例1~2制备的催化剂分别进行了反应评价,表1给出了详细评价结果。
表1催化剂COx甲烷化反应评价结果(反应床层温度200℃的条件下)
由表1的结果可见,本发明实施例催化剂在相同条件下,甲烷化反应COx转化率高于对比例,说明催化剂活性高;并且实施例中的催化剂具有更高的分散度。
Claims (10)
1.一种甲烷化催化剂,以其总重量为百分比计,包含以下组分:
活性组分5~65wt%;
载体35~95wt%;
所述的活性组分选自Ni、Fe、Co中的至少一种。
2.根据权利要求1所述的甲烷化催化剂,其特征在于以其总重量为百分比计,包含以下组分:
活性组分10~60wt%;
载体40~90wt%。
3.根据权利要求1或2所述的甲烷化催化剂,其特征在于:
所述的载体选自氧化铝、氧化锆、稀土氧化物、氧化镁、氧化钡、水滑石、水泥、尖晶石、方镁石、二氧化钛、高岭土、硅藻土、二氧化硅、复合金属氧化物中的至少一种。
4.根据权利要求3所述的甲烷化催化剂,其特征在于:
所述的复合金属氧化物选自Al2O3-SiO2、Al2O3-MgO、Al2O3-TiO2、Al2O3-ZrO2、SiO2-MgO、SiO2-TiO2、SiO2-ZrO2、MgO-TiO2、MgO-ZrO2、TiO2-ZrO2、Al2O3-SiO2-MgO、Al2O3-SiO2-TiO2、Al2O3-SiO2-ZrO2、SiO2-MgO-TiO2、SiO2-MgO-ZrO2、MgO-TiO2-ZrO2、Al2O3-SiO2-MgO-TiO2、Al2O3-SiO2-MgO-ZrO2、SiO2-MgO-TiO2-ZrO2、Al2O3-SiO2-MgO-TiO2-ZrO2中的至少一种。
5.根据权利要求1~4之任一项所述的甲烷化催化剂,其特征在于是将包含所述活性组分对应的可溶性盐、水溶性高分子在内的组分浸渍到载体上经干燥焙烧后而制得。
6.根据权利要求1~5之任一项所述的甲烷化催化剂的制备方法,其特征在于包括以下步骤:
将所述活性组分对应的可溶性盐配置成溶液A;将水溶性高分子配置成溶液B,将A和B完全混合、搅拌均匀后浸渍到载体上,经干燥焙烧后制得所述甲烷化催化剂。
7.根据权利要求6所述的甲烷化催化剂的制备方法,其特征在于:
所述水溶性高分子的用量为所述活性组分和载体的总重量的0.1~10wt%。
8.根据权利要求6所述的甲烷化催化剂的制备方法,其特征在于:
所述的水溶性高分子选自聚乙烯醇、聚丙烯酰胺、聚丙烯酸、聚氧乙烯、聚乙二醇、聚马来酸酐、聚乙烯吡咯烷酮、羧甲基纤维素中的至少一种。
9.根据权利要求6所述的甲烷化催化剂的制备方法,其特征在于:
所述的干燥温度为60~140℃,干燥时间为1~10h;
所述的焙烧温度为250~650℃,焙烧时间为1~10h。
10.根据权利要求6~9之任一项所述的制备方法制成的甲烷化催化剂。
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CN113617358A (zh) * | 2021-09-14 | 2021-11-09 | 润和催化剂股份有限公司 | 一种甲烷化催化剂的制备方法 |
CN113617358B (zh) * | 2021-09-14 | 2023-11-10 | 润和催化剂股份有限公司 | 一种甲烷化催化剂的制备方法 |
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