CN110234428A - 锰掺杂的镍甲烷化催化剂 - Google Patents
锰掺杂的镍甲烷化催化剂 Download PDFInfo
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- CN110234428A CN110234428A CN201880009502.7A CN201880009502A CN110234428A CN 110234428 A CN110234428 A CN 110234428A CN 201880009502 A CN201880009502 A CN 201880009502A CN 110234428 A CN110234428 A CN 110234428A
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- carbon dioxide
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- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
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- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
本发明涉及用于二氧化碳和/或一氧化碳的甲烷化的催化剂，其包含氧化铝、Ni活性物质和Mn，并且其特征在于，催化剂中的Ni/Mn摩尔比为3.0至10.0，优选4.0至9.0并且特别优选5.5至6.5。所述催化剂的特征在于在高选择性和稳定性的情况下的高活性。本发明还涉及用于制备根据本发明的催化剂的方法，包括以下步骤：a)由含有溶解形式的Al、Ni和Mn的溶液共沉淀，以获得沉淀物，b)分离来自步骤a)的沉淀物，c)干燥来自步骤b)的经分离的沉淀物，和d)煅烧来自步骤c)的经干燥的沉淀物。
Description
背景技术
通过所谓的可再生能源光伏和风能供应能量受到由于天气和白昼时间导致的电力生产波动的问题。为了保证供应的安全性，必须找到一种途径来吸收由于天气和白昼时间导致的电力生产的波动。用于以化学方式储存能量的一种潜在方法是电力-气体方法，其中使用过剩电流将水通过电解裂解成氢和氧。其中存储了在电解水之后的能量的氢本身可以仅以高成本存储或运输到最终用户。按照电力-气体方法，氢气因此在另一步骤中与在大气中充当破坏气候的温室气体的二氧化碳在甲烷化反应中转化成甲烷和水。甲烷可以容易地存储在具有数月范围的存储容量的大量现有的基础设施中，可以长距离运输而几乎没有损失，并且可以在需要能量时转换回电力。甲烷化反应与高能量释放相关并且通常以催化方式进行，是所述方法的基石。由反应的高放热性(-165kJ/mol)产生两个直接问题。一方面在高的温度时，热力学平衡限制了可实现的最大甲烷收率。为了将甲烷供入德国的天然气网格，需要95％的纯度。这需要具有高的催化剂活性，从而在工业中使用的反应压力和在低的温度时可以实现更高的甲烷收率。
甲烷化反应的高放热性在绝热的反应器操作时有时在反应器中形成热点。在这种情况下可能局部产生可能损坏催化剂的高的温度。因此令人非常感兴趣的是尽可能开发稳定的催化剂体系，以使催化剂更换/停工时间的成本和材料成本最小化。此外需要尽可能有活性和选择性的用于CO2的甲烷化反应的催化剂。
对于甲烷化反应而言，主要使用镍基催化剂，然而也存在采用其它活性金属，例如钌或铑的方法。作为载体，除了氧化铝之外，还使用硅、钛和锆的氧化物。这样的体系例如描述于公开文献CN104043454A、CN103480375A、CN102091629A、CN104888783A和WO2008110331A1中。
另外，还有不仅含有活性金属，而且还经促进的催化剂。由文献已知，用铁或锰促进可以对催化剂性能产生正面影响。
用锰掺杂例如描述于CN103464163A、CN103752315A、CN102600860A、CN102553610A、CN102527405A、CN102513124A、CN102463120A、CN102463119A、CN103706366、CN104028270和CN101745401中，以及由Zhao等人，Journal of Natural Gas Chemistry(2012)，21(2)，170-177和Gao等人，Journal of molecular catalysis(China)，第25卷，第1期，2011年2月中所描述。
CN103752315A涉及存在于金属载体相上的催化剂，以及所述催化剂通过催化转化一氧化碳和/或二氧化碳制备甲烷或者合成甲烷气体制备的用途和制备方法。存在于金属载体相上的催化剂包含作为活性组分存在于金属载体相上的金属氧化物和辅助金属氧化物，存在于金属载体相上的催化剂的通式为xM1O-yM2O/ZT，其中M1O表示作为活性组分的金属氧化物，ZT表示金属载体相，x表示作为活性组分的金属氧化物在催化剂中的重量百分比份额，和y表示辅助金属氧化物的重量百分比份额。
CN102600860A涉及一种适合于中等或较低温度的合成气的完全甲烷化的催化剂。所述催化剂以重量百分比计包含以下组分：12至26％的镍，1至4％的锰，0.1至2％的来自镧、钙和/或镁中的一种或多种，余量为含有氧化铝和氧化铈的复合载体，其中组分的重量百分比之和为100％，并且复合载体中的氧化铈含量为6至12％。通过如下步骤制备所述催化剂：(1)复合载体的成型；(2)浸渍液的配制；(3)采用加压浸渍法进行处理；(4)对浸渍后的催化剂加热到500至600℃焙烧6至8小时，得到目标产物。
CN102527405A公开了一种高温合成气完全甲烷化催化剂，其中所述催化剂按重量百分比计包含以下成分：10至30重量％的镍，11至20重量％的镧，1至5重量％的铈，0.1至2重量％的来自锰、锂和钒中的一种或多种，并且余量为氧化铝，其中所有这些成分的重量百分比之和为100％。所述催化剂的制备方法包括以下步骤：(1)催化剂组分的组合和混合；(2)干燥，得到熔融物；(3)将熔融物以1至4℃/分钟的加热速度加热至600至800℃，在600至800℃的温度下焙烧6至8小时，得到颗粒物；(4)将颗粒物研磨筛分，采用加压浸渍法进行处理，得到目标产物。
CN102513124A公开了一种通过碳氧化物甲烷化制取人造天然气的技术，并提供了一种用于焦炉煤气甲烷化的催化剂及其制备方法。所述催化剂是γ氧化铝或二氧化钛载体以稳定活性组分和助剂，其中活性组分由Ni组成并且助剂由第一助剂和第二助剂组成；所述第一助剂是稀土元素并且第二助剂是Sr、Mn、V、Zr、Ce和Cr中的一种或几种组合。
CN102463120A公开了一种含镍和锰的催化剂及其制备和应用。含镍和锰的催化剂包含：a)氧化镍，其中镍含量为15至55重量％，和b)氧化锰，其中锰含量为0.1至15重量％。将氧化铝、氧化硅、氧化钛和氧化锆中的至少一种用作催化剂载体。制备方法包括以下步骤：镍盐和锰盐溶解与有机酸溶液互溶，用前一步骤中获得的混合溶液浸渍催化剂载体，在热分解中干燥，获得含镍和锰的催化剂。有机酸溶液是有机羧酸或具有还原性的有机酸，其中有机酸的羧基离子与金属离子的总电荷的摩尔比在0.5至3:1之间，具有还原性的有机酸与金属离子的摩尔比为0.2至2:1。
CN102463119A公开了一种甲烷化催化剂及其制备。所述甲烷化催化剂包含以下组分：a)氧化镍，其中镍含量为5至50重量％；b)氧化锰，其中锰含量为0.1至15重量％；c)选自铍、锰、钙、锶、钡、镧和铈的氧化物中的至少一种，其中金属含量为0.5至20重量％，组分c)分布在整个载体颗粒中。所公开的制备包括以下步骤：1)镍盐和/或锰盐与有机酸互溶，组分c)的盐配成水溶液；2)浸渍待稳定的组分镍、锰和组分c)，其中组分c)单独稳定化，并在每次稳定化之后都经过烘干和焙烧分解处理。
CN103706366描述了一种催化剂，其包含15至55％的活性组分，1至6％的第一催化促进剂，3至15％的第二催化促进剂，余量为催化剂载体，其中活性组分为氧化镍，催化载体为Al2O3，第一催化促进剂选自氧化镧、氧化铈或氧化钐，第二催化促进剂选自氧化镁、氧化锰、氧化铁和氧化锆中的至少一种。制备方法包括以下步骤：将还原剂溶解在水中以获得还原性溶液，将硝酸镍、硝酸铝、第一金属盐和第二金属盐混合到水中以获得原料溶液，并在稳定搅拌下将还原性混合物添加至原料溶液以获得第一溶液，转移至密封反应器并在100至200℃下进行反应10至15小时，冷却至室温，过滤并洗涤至pH值为6至7，在80至120℃下干燥4至30小时，并在300至550℃下煅烧2至12小时以获得催化剂，其中还原剂选自甲醛、水合肼、次亚磷酸钠和抗坏血酸之一，其中第一金属盐为选自硝酸镧，硝酸铈和硝酸钐之一，第二金属盐为选自硝酸镁、硝酸锰、硝酸铁和硝酸锆的至少一种，和碱溶液是碳酸钠，氢氧化钠，碳酸钾，碳酸铵，尿素或NH3*H2O的水溶液。所述催化剂可以与粘合剂(铝酸钙)、润滑剂(石墨)和水混合，然后压制成颗粒形式。该催化剂适合于高温高压煤气甲烷化，以生产合成天然气。
CN104028270公开了一种甲烷化催化剂，其包含基于催化剂的总重量5至60重量％的催化活性的NiO组分，余量包含Al2O3，其还可包含占催化剂总重量的1至25重量％的助剂M，其中助剂组分M选自金属Ce、Ca、Co、La、Sm、Zr、Ba、Mn、Fe、Mo、Ti和Cu的氧化物的一种或多种。该文献还提供了一种制备所述甲烷化催化剂的方法，包括将催化活性组分的前体、助剂组分M的前体以及催化剂载体的前体按照对应甲烷化催化剂的组成的比例混合，加入有机燃料混合均匀并干燥，以形成凝胶状产物，进行燃烧反应，清洗和干燥，以获得最终产品。
CN101745401公开了一种负载型耐硫甲烷化催化剂，其特征在于，催化剂以主金属M为活性组分，第二金属M1作为助剂，S作为载体材料，其中M1、M和S的重量比为0.01-39:1-30:0.01-90，M是Mo、W和/或V，第二金属M1是Fe、Co、Ni、Cr、Mn、La、Y或/和Ce的一种或多种，并且载体S是ZrO2、Al2O3、MgO或TiO2。通过溶胶-凝胶法制备所述负载型耐硫甲烷化催化剂。
发明内容
本发明的任务在于提供用于一氧化碳和/或二氧化碳的甲烷化的催化剂，所述催化剂在高的选择性和稳定性的情况下具有与现有技术的催化剂相比改进的活性。
该任务通过用于一氧化碳和/或二氧化碳的甲烷化的催化剂得以解决，所述催化剂包含氧化铝、Ni活性物质以及Mn，其中催化剂中的Ni/Mn摩尔比为3.0至10.0，优选4.0至9.0并且特别优选5.5至6.5。
Ni/Mn比例还可以在6.0至10.0范围内，优选在7.0至9.0范围内，非常特别优选在7.5至8.5范围内。
氧化铝不必为化学计量的Al2O3，而是在这种情况下还可以为非化学计量的氧化铝。
促进剂Mn可以完全或部分地包含在Ni活性物质中。催化剂除了Mn以外还可以含有另外的促进剂，但也可以仅含有促进剂Mn。Al、Ni以及促进剂的氧化态可以根据催化剂的处理而变化。Al、Ni和促进剂典型地以金属阳离子(例如Al3+、Ni2+、Mn2+、Mn3+、Mn4+)形式存在。在煅烧(例如在空气中)之后，可以达到高的氧化态或者最高氧化态。如果将催化剂在高于室温的温度，例如在反应条件下用氢气还原，则Al、Ni和促进剂可以呈现较低的氧化态或者部分地或完全地以氧化态0出现。金属阳离子的电荷平衡由氧阴离子(O2-)实现。
除了氧化铝(AlOx，其中x≤1.5)、Ni和Mn(以及电荷平衡所需要的氧阴离子)以外，根据本发明的催化剂可以含有另外的组分，但是其也可以仅由氧化铝、Ni和Mn组成。同样，除了Mn以外，Ni活性物质也可以含有另外的促进剂，例如Fe，但其也可以仅含有促进剂Mn。优选地，Ni活性物质不含有选自Ta、In、Cu、Ce、Cr、Bi、Fe、P、Sb、Sn、B、Si、Ti、Zr、Co、Rh、Ru、Ag、Ir、Pd和Pt的元素。优选地，Ni活性物质不含有贵金属。
Al/Ni原子比可以在介于0.5与1.5之间，优选介于0.8与1.2之间；Al/Ni比例特别优选接近1。
根据本发明的催化剂可以有利地具有直径低于20nm，优选低于10nm的Ni活性物质微晶。Ni活性物质还可以完全或大部分由直径低于20nm，优选低于10nm的微晶组成。Ni活性物质优选以金属态存在。
催化剂的CO2吸收容量在35℃时可以为大于150μmol/g并且优选在介于150至350μmol/g范围内，特别优选介于180至260μmol/g。
根据本发明的催化剂的BET表面积(SBET)可以为大于100m2/g，优选大于200m2/g，或在200至400m2/g范围内，优选在200至300m2/g范围内并且尤其优选在200至250m2/g范围内。
根据本发明的催化剂的比金属表面积(Smet)优选为大于5m2/g，优选大于10m2/g，或在10至30m2/g范围内，优选在15至25m2/g范围内或在17至23m2/g范围内。
此外，本发明涉及用于制备甲烷化催化剂的方法，包括以下步骤：
a)由含有溶解形式的Al、Ni和Mn的溶液共沉淀，以获得沉淀物，
b)分离来自步骤a)的沉淀物，
c)干燥来自步骤b)的经分离的沉淀物，和
d)煅烧来自步骤c)的经干燥的沉淀物。
在此优选的是，来自步骤a)的溶液是水溶液，以及Al、Ni和Mn在水溶液中以溶解方式作为离子化合物存在。
Al优选以溶解方式作为硝酸铝、三氯化铝或硫酸铝存在。Ni优选以溶解方式作为硝酸镍、二氯化镍、硫酸镍、乙酸镍或碳酸镍存在。Mn优选以氧化态II或IV存在并且作为硝酸锰、乙酸锰、二氯化锰、硫酸锰溶解或者还以氧化态VII作为高锰酸根离子溶解。
通过将含有Al、Ni和Mn的溶液加入预置的碱性溶液或通过将碱性溶液添加至预知的含有Al、Ni和Mn的溶液而进行共沉淀。或者，将含有Al、Ni和Mn的溶液与碱性溶液同时添加至容器中，所述容器可以已经含有溶剂，如水，并且在其中混合。碱性溶液具有大于7，优选在8至10范围内的pH，以及优选含有碱金属氢氧化物和/或碱金属碳酸盐，例如氢氧化钠和碳酸钠的混合物。共沉淀优选在控温下进行，使得溶液的温度接近室温或例如为30℃。
优选地，Al、Ni和Mn以溶解形式作为离子化合物存在于水溶液中，和具有相同的阴离子，所述阴离子可以为例如硝酸根。
在通过共沉淀进行沉淀之后，优选使沉淀物在溶液中陈化至少30分钟，优选长于1小时，更优选长于12小时。优选如此进行陈化：将沉淀物在接近室温的情况下在搅拌下留在溶液(母液)中。
分离通过共沉淀获得的沉淀物，这例如通过过滤而进行。过滤可以以合适的方式例如通过压滤机进行。
优选洗涤经分离的沉淀物，例如采用蒸馏水洗涤，直至达到中性pH值。
接下来可以干燥经分离的沉淀物，例如在升高的温度在空气中干燥。优选地，干燥在介于70℃与90℃之间的温度经长于4小时，优选长于12小时的时间段。
煅烧经分离的沉淀物，这可以在空气中在介于300℃至600℃的温度，优选在400℃至500℃，和在3小时至10小时，优选5至7小时的时间段内进行。
根据本发明的催化剂应当尤其用于一氧化碳和/或二氧化碳的甲烷化中。二氧化碳的甲烷化能够通过以下反应方程表示：
4H2+CO2-->CH4+2H2O
一氧化碳的甲烷化能够通过以下反应方程表示：
3H2+CO-->CH4+H2O
在用于进行甲烷化的方法中，使含有二氧化碳和/或一氧化碳或二者的混合物的反应气体在高于200℃的温度与催化剂接触。
附图说明
图1至4显示了锰掺杂的催化剂Mn1、Mn4、Mn6和Mn8在陈化之前和之后的催化行为。
图1：Mn1(对比实施例)的催化测试结果。
图2：Mn4(实施例)的催化测试结果。
图3：Mn6(实施例)的催化测试结果。
图4：Mn8(对比实施例)的催化测试结果。
图5：所描述的样品的活性/稳定性图。
具体实施方式
方法
元素分析
经煅烧的催化剂的组成的测定通过电感耦合等离子体发射光谱(ICP-OES)进行。将50mg催化剂在60℃溶于50ml的1摩尔的磷酸(VWR，分析纯)中。为了溶解形成的二氧化锰，向溶液添加50mg的Na2SO3(Sigma-Aldrich，分析纯)。在冷却之后，将溶液以1/10稀释，并且借助0.1μm过滤器(Pall)过滤。将校正溶液准备为1、10和50mg l-1(Merck)。借助Agilent700ICP-OES进行金属浓度的测定。
比表面积的测定
催化剂的比表面积(SBET)的测定借助N2-BET分析在Nova 4000e(Quantachrome)上进行。为此，使100mg催化剂在120℃脱气3小时，然后在0.007至1的p/p0范围内记录吸附等温线和解吸等温线。为了测定BET表面积，考虑在0.007至0.28的p/p0范围内的数据点。
化学吸附
化学吸附实验在Autosorb 1C(Quantachrome)上进行。在测量之前，将100mg催化剂在500℃于10％的在N2中的H2中活化6小时。加热斜率为2K min-1。
金属表面积(SMET)的测定按照DIN 66136-2(版本：2007-01)进行并且借助H2化学吸附在35℃进行。为此从40mmHg至800mmHg等距记录20个吸附点。吸附的平衡时间为2min，热平衡的平衡时间为10min。对于测定金属表面积，设定金属原子/H化学计量比为1。对于用于测定CO2吸收容量(U(CO2))的CO2化学吸附测量，在其它参数不变的情况下将平衡时间设定为10min。在记录化学吸附数据之前，通过实验排除在这些条件下对CO2化学吸附的任何动力学抑制。金属表面积和CO2吸收容量根据外推法外推至0mmHg的压力。
合成
通过共沉淀制备催化剂并且将镍与铝的原子比设定至1。为了研究铁对催化剂行为的影响，在催化剂合成期间将硝酸铁(III)添加至硝酸镍和硝酸铝的盐溶液。为了研究铁和锰对催化剂行为的同时影响，在催化剂合成期间将硝酸锰(II)和硝酸铁(III)添加至硝酸镍和硝酸铝的盐溶液。所有使用的化学品的纯度为分析纯。将水通过Millipore过滤器系统纯化以及借助电导率测量验证纯度。在双壁的3L容量的搅拌釜反应器中进行合成。用水填充的双夹套能够通过恒温器将合成运行控温在30℃，两个挡板有助于更好的混合。对于搅拌，可以以150转每分钟使用KPG(精密玻璃)搅拌器。为了合成，在搅拌式反应釜中预置1LH2O，并且调节至pH 9±0.1。溶解的硝酸盐的混合物的计量添加以2.5ml min-1进行。同时使用沉淀试剂的受控添加，以维持pH值。作为起始物质，使用各种硝酸盐(Ni(NO3)2*6H2O、Al(NO3)2*9H2O、Fe(NO3)3*9H2O和Mn(NO3)2*4H2O)的一摩尔溶液。将它们如表2中所示混合成120ml min-1的总体积，然后滴加至反应器中。作为沉淀试剂，使用0.5M NaOH和0.5M Na2CO3溶液的等体积混合物，将滴定仪用于其计量添加。在持续搅拌下将悬浮液在母液中陈化过夜，然后过滤沉淀物并且将其用H2O洗涤，直至滤液具有中性pH值。在80℃在干燥烘箱中干燥过夜之后，将经干燥的沉淀物(前体)以5K min-1的加热速率加热至450℃，并且在合成空气中煅烧6小时。
活性测量和稳定性测量
为了能够对比不同催化剂关于CO2甲烷化的活性，开发了报告其活性和稳定性的测试程序。为此将25mg筛分级分为150-200μm的催化剂用9倍量的SiC稀释并且引入反应器中。如表1中详述进行相继的测量步骤：还原、平衡、S-曲线1、陈化和S-曲线2。
表1：测定活性曲线和稳定性曲线的测量步骤的参数
为了测定温度-CO2转化率曲线，将温度在给定范围内逐步以25℃的增量升高并且分别测定活性。在32小时在500℃的陈化之前和之后的两个S曲线的对比允许了解体系关于高的温度的稳定性。
作为活性的量度，代表性地测定在S曲线1测量步骤期间达到75％的CO2转化率所必需的温度T75.1。为此将温度在给定范围内逐步以25℃的增量升高。T75.1越低，则因此催化剂的活性越高。
作为陈化之后的活性的量度，代表性地测定在S曲线2测量步骤期间达到75％的CO2转化率所必需的温度T75.2。为此将温度在给定范围内逐步以25℃的增量升高。T75.2越低，则因此催化剂在陈化之后的活性越高。
如果由两个转化温度特征计算T75.1与T75.2之间的差异，则获得对催化剂的稳定性的度量。还适用的是，差异越小则催化剂越稳定。为了更好的可比性，将所有测定的活性和稳定性归一化至未促进的镍-氧化铝催化剂(Ni)。归一化的活性和稳定性由以下给出：
图1至4中的结果显示，用锰促进Ni/AlOx催化剂导致催化剂活性的明显提高。
实施例
表2：在共沉淀中使用的单摩尔金属盐溶液
表3：经煅烧的催化剂的组成
表4：催化剂的表征
*归一化至经煅烧的催化剂的质量表5：催化测试反应的结果
Claims (14)
1.用于一氧化碳和/或二氧化碳的甲烷化的催化剂，其包含氧化铝、Ni活性物质和Mn，其特征在于，催化剂中的Ni/Mn摩尔比为3.0至10.0，优选4.0至9.0并且特别优选5.5至6.5。
2.根据权利要求2所述的催化剂，其特征在于，所述Ni活性物质具有直径低于20mm，优选低于10nm的微晶。
3.根据前述权利要求任一项所述的催化剂，其特征在于在35℃时大于200μmol/g，优选200至300μmol/g的CO2吸收容量。
4.根据前述权利要求任一项所述的催化剂的用途，用于一氧化碳和/或二氧化碳与气态氢气的甲烷化。
5.用于制备根据权利要求1所述的催化剂的方法，包括以下步骤：
a)由含有溶解形式的Al、Ni和Mn的溶液共沉淀，以获得沉淀物，
b)分离来自步骤a)的沉淀物，
c)干燥来自步骤b)的经分离的沉淀物，和
d)煅烧来自步骤c)的经干燥的沉淀物。
6.根据权利要求5所述的方法，其特征在于，来自步骤a)的溶液是水溶液。
7.根据权利要求5或6所述的方法，其特征在于，使所述沉淀物在溶液中陈化至少30分钟。
8.根据权利要求5至7所述的方法，其特征在于，洗涤来自步骤b)的经分离的沉淀物。
9.根据权利要求5至8所述的方法，其特征在于，所述溶解形式的Al、Ni和Mn作为离子化合物存在于溶液中，和所述离子化合物具有相同的阴离子。
10.根据权利要求9所述的方法，其特征在于，所述阴离子为硝酸根、硫酸根、卤素离子、氯离子或乙酸根。
11.根据权利要求5至10任一项所述的方法，其特征在于，来自步骤a)的溶液中的Mn以氧化态II或III存在。
12.根据权利要求11所述的方法，其特征在于，所述经干燥的沉淀物的煅烧在300至600℃的温度在空气中进行。
13.用于二氧化碳和/或一氧化碳的甲烷化的方法，其中使含有二氧化碳和/或一氧化碳的气体与根据权利要求1所述的催化剂接触。
14.根据权利要求13所述的方法，其中使所述气体与所述催化剂在高于200℃的温度接触。
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| CN114917921A (zh) * | 2022-06-08 | 2022-08-19 | 珠海格力电器股份有限公司 | 一种NiMnAl类水滑石催化剂及其制备方法和应用 |
| CN116060049A (zh) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | 一种加氢催化剂及其制备方法和应用 |
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| US11261137B2 (en) * | 2018-03-09 | 2022-03-01 | Clariant International Ltd | Manganese-doped nickel methanization catalysts having elevated sulphur resistance |
| CN110639543A (zh) * | 2019-09-30 | 2020-01-03 | 四川蜀泰化工科技有限公司 | 一种甲烷化催化剂及其制备方法 |
| CN111495374B (zh) * | 2020-05-13 | 2023-07-28 | 黄冈师范学院 | 一种包覆型CoNi/Al2O3催化剂、其制备方法及应用 |
| CN115672331A (zh) * | 2021-07-23 | 2023-02-03 | 国家能源投资集团有限责任公司 | 甲烷化催化剂及其制备方法和应用 |
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| Publication number | Publication date |
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| EP3576871A1 (de) | 2019-12-11 |
| US20190381486A1 (en) | 2019-12-19 |
| JP2020505227A (ja) | 2020-02-20 |
| WO2018141649A1 (de) | 2018-08-09 |
| JP6830543B2 (ja) | 2021-02-17 |
| EP3576871B1 (de) | 2021-07-28 |
| US10888846B2 (en) | 2021-01-12 |
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