CN112619654A - 一种甲烷二氧化碳重整制合成气的催化剂及其制备方法 - Google Patents
一种甲烷二氧化碳重整制合成气的催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 238000002407 reforming Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229910003023 Mg-Al Inorganic materials 0.000 claims abstract description 14
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 14
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 14
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012072 active phase Substances 0.000 claims abstract description 4
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 59
- 239000012065 filter cake Substances 0.000 claims description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 22
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- 239000004202 carbamide Substances 0.000 claims description 16
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KDRIEERWEFJUSB-UHFFFAOYSA-N carbon dioxide;methane Chemical compound C.O=C=O KDRIEERWEFJUSB-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
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- 238000001816 cooling Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
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- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 claims description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
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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
- B01J23/78—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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Abstract
本发明公开了一种甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,以Ni、Co为活性相,ZrO2为助剂,通过均匀共沉淀法合成Ni‑Co‑Zr‑Mg‑Al HTLcs类水滑石前驱体,然后经过焙烧得到Ni‑Co/ZrO2/Mg(Al)O催化剂。本发明提供的甲烷二氧化碳重整制合成气的催化剂的制备方法制备的催化剂具有过程简单、活性高、寿命长等特点。
Description
技术领域
本发明属于二氧化碳及甲烷利用技术领域,具体涉及一种用于甲烷二氧化碳重整制合成气的催化剂的制备方法。
背景技术
近年来,全球变暖成为广大科研工作者关注的主要问题。甲烷(CH4)和二氧化碳(CO2)是主要的温室气体,甲烷与二氧化碳重整反应不仅有效利用了两种温室气体,而且是制合成气的有效途径之一,制得的合成气可用于二甲醚合成、羰基合成、费托合成等,对于缓解化工原料和能源危机具有重大意义。
专利CN 201410604642.2公开了一种甲烷二氧化碳重整反应中的 Pt-ZrO2/WC催化剂,该催化剂呈层状结构,内层为载体,包括Al2O3、MgO、SiO2、 TiO2、ZrO2、泡沫陶瓷、稀土金属氧化物、复合氧化物或碳/碳复合材料,中间层为WC层,最外层为Pt-ZrO2层。所得催化剂虽然阻止了碳的生成,保持了催化剂的稳定性,但最外层负载贵金属Pt,存在资源有限、价格昂贵等缺点。
专利CN 201410652362.9公开了一种甲烷与二氧化碳重整制合成气的催化剂及其制备方法,该催化剂以活性炭为载体,通过氨水浸泡、微波辐射改性制作成电极,再通过电吸附法制得Co-Ni-Zr-K-Mg/AC催化剂。该催化剂制备过程复杂,不易于大规模工业化生产。
在甲烷二氧化碳重整反应中,贵金属催化剂表现出良好的催化性能和抗积碳性能,但存在成本高、回收困难等问题;在非贵金属催化剂中,Ni作为重整催化剂催化活性最高,而且价格相对低廉,但Ni基催化剂积炭较为严重,难于克服。因此,开发高效、抗积炭和稳定性好的催化剂是实现甲烷二氧化碳重整反应工业化最急需解决的问题。
发明内容
本发明所要解决的技术问题是:在甲烷二氧化碳重整反应所采用的贵金属催化剂存在成本高、回收困难,而非贵金属催化剂中,Ni基催化剂积炭严重的问题。
为了解决上述技术问题,本发明提供了一种甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,以Ni、Co为活性相,ZrO2为助剂,通过均匀共沉淀法合成Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体,然后经过焙烧得到 Ni-Co/ZrO2/Mg(Al)O催化剂。
优选地,所述制备方法,包括以下步骤:
步骤1):将Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Zr(NO3)4·5H2O、Mg(NO3)2·6H2O 和Al(NO3)3·9H2O溶于去离子水中配成混合盐溶液,然后加入尿素溶解;搅拌条件下,再加入乙二胺形成混合溶液;
步骤2):将步骤1)得到的混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中密封,置于烘箱中恒温反应24-48h;取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼;
步骤3):将步骤2)所得滤饼在丙酮中分散,然后重复3次过滤、分散,最后过滤,用乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;
步骤4):将Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
更优选地,所述步骤1)中Al3+与Ni2+、Co2+、Mg2+和Al3+的总摩尔比为 0.2-0.33:1,Zr4+与Ni2+的摩尔比为0.003-0.01:1,Co2+与Ni2+的摩尔比为 0.005-0.015:1。
更优选地,所述步骤1)中尿素与混合盐溶液中硝酸根的摩尔比为3-4:1。
更优选地,所述步骤1)中乙二胺的加入量为混合溶液体积的1%-5%。
更优选地,所述步骤2)中烘箱的温度为95℃。
更优选地,所述步骤3)中每次分散滤饼丙酮的用量为滤饼质量的10-20倍,每次洗涤滤饼乙醇的用量为滤饼质量的2-5倍。
更优选地,所述步骤3)中干燥的温度为80℃,时间12h。
更优选地,所述步骤4)中焙烧的温度为700℃,时间为5h。
本发明提供的甲烷二氧化碳重整制合成气的催化剂的制备方法制备的催化剂具有过程简单、活性高、寿命长等特点。
与现有技术相比,本发明具有如下优点:
(1)本发明采用均匀共沉淀法合成Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体,其层板上二价、三价金属离子受晶格能和定位效应的影响,Ni和Co金属离子在前驱体中保持高度、均匀分散;
(2)在共沉淀时加入乙二胺,使二价、三价离子与乙二胺形成配位离子,有效控制晶粒尺寸,防止团聚,分散性良好;
(3)通过丙酮分散提高Ni-Co/ZrO2/Mg(Al)O催化剂比表面积,提高甲烷二氧化碳重整反应活性和稳定性。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,作详细说明如下。
对实施例中制得的Ni-Co/ZrO2/Mg(Al)O催化剂用于甲烷二氧化碳重整反应评价过程如下:
称取0.1g(80-100目)与石英砂0.9g(80-100目)混合均匀,于H2/N2气氛 (体积百分比各50%,流速120mL/min)、700℃预还原1h。还原完毕后,在还原气氛下将反应温度提升至850℃,温度升至850℃后,切换成CO2/CH4混合气 (摩尔比1.2:1,GHSV=80000mL/g-cat·h)进行甲烷二氧化碳反应。反应后的气体经冷却后,使用岛津GC-2014气相色谱仪进行分析,采用内标法计算CO2和CH4转化率,同时计算反应后气体中H2与CO的摩尔比。
实施例1
按Al3+:(Ni2++Co2++Mg2++Al3+)的摩尔比为0.2:1、Zr4+:Ni2+摩尔比为0.003 和Co2+:Ni2+摩尔比为0.005:1,分别称取19.1631g Ni(NO3)2·6H2O、0.09589g Co(NO3)2·6H2O、0.0849g Zr(NO3)4·5H2O、8.4487g Mg(NO3)2·6H2O和9.2657g Al(NO3)3·9H2O溶于250mL去离子水中,搅拌使硝酸盐完全溶解,得到混合盐溶液。按尿素与混合盐溶液中硝酸根的摩尔比为3:1,将16.4114g尿素溶解于混合盐溶液中。然后在搅拌速度为400rpm下加入12.5mL乙二胺,形成混合溶液。将此混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中,密封反应釜,置于烘箱中恒温反应24h。取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼。将所得滤饼在10倍质量的丙酮中分散1h,过滤,再用10倍质量丙酮分散,共3次。最后过滤,用滤饼2倍质量的乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;再在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
将此催化剂用于甲烷二氧化碳重整反应,评价结果为:连续运行800h后, CO2转化率89.36%,CH4转化率94.02%,反应后气体中H2与CO摩尔比为:0.89: 1。
实施例2
按Al3+:(Ni2++Co2++Mg2++Al3+)的摩尔比为0.33:1、Zr4+:Ni2+摩尔比为0.01: 1和Co2 +:Ni2+摩尔比为0.015,分别称取19.1631g Ni(NO3)2·6H2O、0.2877g Co(NO3)2·6H2O、0.2829g Zr(NO3)4·5H2O、5.6325g Mg(NO3)2·6H2O和16.4157g Al(NO3)3·9H2O溶于250mL去离子水中,搅拌使硝酸盐完全溶解,得到混合盐溶液。按尿素与混合盐溶液中硝酸根的摩尔比为4:1,将18.7163g尿素溶解于混合盐溶液中。然后在搅拌速度为400rpm下加入25mL乙二胺,形成混合溶液。将此混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中,密封反应釜,置于烘箱中恒温反应24h。取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼。将所得滤饼在20倍质量的丙酮中分散1h,过滤,再用20倍质量丙酮分散,共3次。最后过滤,用滤饼5倍质量的乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;再在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
将此催化剂用于甲烷二氧化碳重整反应,评价结果为:连续运行800h后, CO2转化率88.23%,CH4转化率93.41%,反应后气体中H2与CO摩尔比为:0.88: 1。
实施例3
按Al3+:(Ni2++Co2++Mg2++Al3+)的摩尔比为0.3:1、Zr4+:Ni2+摩尔比为0.006: 1和Co2 +:Ni2+摩尔比为0.01:1,分别称取19.1631g Ni(NO3)2·6H2O、0.1938g Co(NO3)2·6H2O、0.1700g Zr(NO3)4·5H2O、17.0769g Mg(NO3)2·6H2O和21.4199g Al(NO3)3·9H2O溶于250mL去离子水中,搅拌使硝酸盐完全溶解,得到混合盐溶液。按尿素与混合盐溶液中硝酸根的摩尔比为3.3:1,将26.3793g尿素溶解于混合盐溶液中。然后在搅拌速度为400rpm下加入3.75mL乙二胺,形成混合溶液。将此混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中,密封反应釜,置于烘箱中恒温反应36h。取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼。将所得滤饼在12倍质量的丙酮中分散1h,过滤,再用12倍质量丙酮分散,共3次。最后过滤,用滤饼3倍质量的乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;再在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
将此催化剂用于甲烷二氧化碳重整反应,评价结果为:连续运行800h后, CO2转化率90.54%,CH4转化率95.67%,反应后气体中H2与CO摩尔比为:0.89: 1。
实施例4
按Al3+:(Ni2++Co2++Mg2++Al3+)的摩尔比为0.25:1、Zr4+:Ni2+摩尔比为0.08: 1和Co2 +:Ni2+摩尔比为0.007:1,分别称取19.1631g Ni(NO3)2·6H2O、0.1343g Co(NO3)2·6H2O、2.2633g Zr(NO3)4·5H2O、25.3461g Mg(NO3)2·6H2O和20.6697g Al(NO3)3·9H2O溶于250mL去离子水中,搅拌使硝酸盐完全溶解,得到混合盐溶液。按尿素与混合盐溶液中硝酸根的摩尔比为3.5:1,将31.0396g尿素溶解于混合盐溶液中。然后在搅拌速度为400rpm下加入7.5mL乙二胺,形成混合溶液。将此混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中,密封反应釜,置于烘箱中恒温反应48h。取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼。将所得滤饼在15倍质量的丙酮中分散1h,过滤,再用15倍质量丙酮分散,共3次。最后过滤,用滤饼4倍质量的乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;再在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
将此催化剂用于甲烷二氧化碳重整反应,评价结果为:连续运行800h后, CO2转化率89.16%,CH4转化率94.58%,反应后气体中H2与CO摩尔比为:0.89:1。
实施例5
按Al3+:(Ni2++Co2++Mg2++Al3+)的摩尔比为0.3:1、Zr4+:Ni2+摩尔比为0.05: 1和Co2 +:Ni2+摩尔比为0.009:1,分别称取19.1631g Ni(NO3)2·6H2O、0.1726g Co(NO3)2·6H2O、1.4146g Zr(NO3)4·5H2O、33.7948g Mg(NO3)2·6H2O和31.8861g Al(NO3)3·9H2O溶于250mL去离子水中,搅拌使硝酸盐完全溶解,得到混合盐溶液。按尿素与混合盐溶液中硝酸根的摩尔比为3.3:1,将39.9258g尿素溶解于混合盐溶液中。然后在搅拌速度为400rpm下加入12.5mL乙二胺,形成混合溶液。将此混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中,密封反应釜,置于烘箱中恒温反应48h。取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼。将所得滤饼在12倍质量的丙酮中分散1h,过滤,再用12倍质量丙酮分散,共3次。最后过滤,用滤饼5倍质量的乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;再在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
将此催化剂用于甲烷二氧化碳重整反应,评价结果为:连续运行800h后, CO2转化率88.75%,CH4转化率93.83%,反应后气体中H2与CO摩尔比为:0.89: 1。
对比例1
按Al3+:(Ni2++Co2++Mg2++Al3+)的摩尔比为0.3:1、Zr4+:Ni2+摩尔比为0.006: 1和Co2 +:Ni2+摩尔比为0.01:1,分别称取19.1631g Ni(NO3)2·6H2O、0.1938g Co(NO3)2·6H2O、0.1700g Zr(NO3)4·5H2O、17.0769g Mg(NO3)2·6H2O和21.4199g Al(NO3)3·9H2O溶于250mL去离子水中,搅拌使硝酸盐完全溶解,得到混合盐溶液。按尿素与混合盐溶液中硝酸根的摩尔比为3.3:1,将26.3793g尿素溶解于混合盐溶液中。将此混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中,密封反应釜,置于烘箱中恒温反应36h。取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼。将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-AlHTLcs 类水滑石前驱体;再在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
将此催化剂用于甲烷二氧化碳重整反应,评价结果为:连续运行800h后, CO2转化率67.13%,CH4转化率70.67%,反应后气体中H2与CO摩尔比为:0.87: 1。
表1为实施例3与对比例1催化剂性能对比。从表中可以看出,实施例3在 Ni-Co/ZrO2/Mg(Al)O催化剂制备过程中添加了乙二胺,并且采用丙酮和乙醇溶剂洗涤催化剂,得到的催化剂稳定性良好,运行800h后CO2和CH4转化率无明显下降趋势;而对比例1中,未添加乙二胺,未采用丙酮和乙醇洗涤,得到的催化剂比表面仅为实施例3中的71.2%,平均粒径长大2.42倍,并且对比例1中的催化剂性能不稳定,虽然24h活性和对比例3相差不大,但经过800h运行后,CO2转化率下降到67.13%,CH4转化率下降到70.67%,远低于实施例3运行至800h 时催化剂性能;实施例3合成得到的催化剂,反应后尾气中H2/CO摩尔比也很稳定,800h内维持在0.89:1,而对比例1合成的催化剂反应后尾气中H2/CO摩尔呈缓慢下降趋势,从0.89:1下降到0.87:1。总而言之,采用均匀共沉淀法合成催化剂的过程中,通过乙二胺配位作用和有机溶剂丙酮、乙醇的分散作用,制得的催化剂表面积增大,粒径减小,稳定性显著增强,H2/CO摩尔比适中,合成过程简单、可控,具有工业化应用前景。
表1
Claims (9)
1.一种甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,以Ni、Co为活性相,ZrO2为助剂,通过均匀共沉淀法合成Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体,然后经过焙烧得到Ni-Co/ZrO2/Mg(Al)O催化剂。
2.如权利要求1所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,包括以下步骤:
步骤1):将Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Zr(NO3)4·5H2O、Mg(NO3)2·6H2O和Al(NO3)3·9H2O溶于去离子水中配成混合盐溶液,然后加入尿素溶解;搅拌条件下,再加入乙二胺形成混合溶液;
步骤2):将步骤1)得到的混合溶液转入内衬为聚四氟乙烯的不锈钢反应釜中密封,置于烘箱中恒温反应24-48h;取出反应釜,冷却至室温,过滤,用去离子水洗涤至滤液呈中性,得滤饼;
步骤3):将步骤2)所得滤饼在丙酮中分散,然后重复3次过滤、分散,最后过滤,用乙醇洗涤滤饼2-3次,将所得滤饼在烘箱中干燥得Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体;
步骤4):将Ni-Co-Zr-Mg-Al HTLcs类水滑石前驱体在马弗炉中焙烧后,得到Ni-Co/ZrO2/Mg(Al)O催化剂。
3.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤1)中Al3+与Ni2+、Co2+、Mg2+和Al3+的总摩尔比为0.2-0.33:1,Zr4+与Ni2+的摩尔比为0.003-0.01:1,Co2+与Ni2+的摩尔比为0.005-0.015:1。
4.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤1)中尿素与混合盐溶液中硝酸根的摩尔比为3-4:1。
5.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤1)中乙二胺的加入量为混合溶液体积的1%-5%。
6.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤2)中烘箱的温度为95℃。
7.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤3)中每次分散滤饼丙酮的用量为滤饼质量的10-20倍,每次洗涤滤饼乙醇的用量为滤饼质量的2-5倍。
8.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤3)中干燥的温度为80℃,时间12h。
9.如权利要求2所述的甲烷二氧化碳重整制合成气的催化剂的制备方法,其特征在于,所述步骤4)中焙烧的温度为700℃,时间为5h。
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