CN110813302A - 一种Ni基催化剂的制备方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 238000000034 method Methods 0.000 claims abstract description 15
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 12
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
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- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 150000002431 hydrogen Chemical class 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000002407 reforming Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 238000005470 impregnation Methods 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种Ni基催化剂的制备方法,该方法以柠檬酸、硝酸铈或硝酸镧、硝酸钙、硝酸镍为原料,经过水浴加热形成湿凝胶后,采用微波煅烧法直接加热湿凝胶快速合成Ni基催化剂Ni/CaO‑CeO2或Ni/CaO‑La2O3;本发明制备的催化剂在中低温下对乙醇重整制氢的催化活性和稳定性均较好,450℃就能使乙醇转化率达到100%,20Ni/CaO‑10CeO2催化剂在550℃连续反应200h乙醇转化率还能保持100%;与传统马弗炉煅烧法制备的催化剂相比,本发明方法制备的催化剂对氢气的选择性更好,并且本发明方法中催化剂的合成时间短和能耗低,从而大大降低生产成本,这也为醇类重整制氢催化剂的工业化进程开辟了一条新的途径。
Description
技术领域
本发明涉及化工技术领域,具体涉及一种Ni基催化剂的制备方法及其在乙醇水蒸气重整制氢中的应用。
背景技术
乙醇是一种低毒、早已工业化生产和易储存的可再生能源,其水蒸气重整制氢已然成为氢能源开发中的热点。因价格低廉、催化性能优越,镍基催化剂被广泛应用于乙醇水蒸气重整制氢反应的研究。然而镍基催化剂稳定性较差,容易因烧结、积碳而失活。目前解决的方法大多是选择合适的载体,或者在其基础上添加助剂来改善镍基催化剂的稳定性。目前常用的载体有碱性材料(ZnO、CaO、MgO等)、两性材料(A1203、Ti02、Ce02等)、酸性材料(硅藻土、沸石等)、中性材料(石棉、活性炭等),但单一组分载体总存在着稳定性不高、选择性差亦或是抗积碳性能低等缺陷(如Ni-A1203催化剂因A1203酸性位点较多催化剂容易积碳而失活)。在单一组分的镍基催化剂中添加助剂(如Ce02、La2O3等)可以很好的调节载体酸碱性从而达到提高催化剂稳定性及活性的目的,但总的来说,目前还没有找到一种稳定性及活性相对较好适合工业大规模生产的镍基催化剂。
在催化剂中添加助剂(如Ce02、La2O3等)来改性镍基催化剂的方法有很多,常规的做法都是浸渍法、共沉淀或者说共沉淀以后再浸渍,这些方法基本上都存在制备工艺繁琐或者难控制、制备条件苛刻等问题,而且成本较高,这也在一定程度上制约了当前催化剂在工业醇类制氢中的应用。
发明内容
针对现有技术存在的合成工序复杂及合成成本高的缺陷,本发明提供一种制备方法简单、成本低及性能优良的Ni基催化剂的制备方法。
本发明方法步骤如下:
(1)将硝酸铈或硝酸镧、硝酸钙、硝酸镍加入去离子水中,搅拌至完全溶解,然后将柠檬酸添加到上述混合溶液中,搅拌至完全溶解;
所述硝酸镍与柠檬酸的质量比为1:3.4-9.5;
(2)将步骤(1)溶液置于75-85℃下水浴加热4-5h,得到湿凝胶;
(3)将步骤(2)湿凝胶置于微波马弗炉中在微波、800-850℃下煅烧30-60min,降温至室温后取出,制得Ni基催化剂Ni/CaO-CeO2或Ni/CaO-La2O3,其中Ni的含量为8-20%,CeO2或La2O3含量为5-15%,CaO含量为87-65%;
所述升温速率为10℃/min,降温速率为10℃/min。
本发明另一目的是将上述方法制得的Ni基催化剂应用在氢气制备中,即以乙醇、水蒸气为原料,以Ni基催化剂为催化剂,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,在450-700℃、0.3MPa下制得氢气。
本发明与现有技术相比具有的突出效果为:
1、采用微波直接加热煅烧湿凝胶较固体催化剂加热受热更均匀,并且合成的Ni基催化剂性能较好,为当前制备催化剂的择优选取提供了借鉴价值;
2、本发明方法制得的催化剂催化性能和稳定性好,而且制备工序简单,能耗低,节省了将近80%制备时间;
3、本发明制备的催化剂同样适用于其它制氢的反应中,真正实现了催化剂的多领域应用。
附图说明
图1是微波制备的20Ni/CaO-10CeO2-W催化剂和传统煅烧法制备的20Ni/CaO-10CeO2-C催化剂乙醇转化率对比图;
图2是微波制备的20Ni/CaO-10CeO2-W催化剂和传统煅烧法制备的20Ni/CaO-10CeO2-C催化剂氢气选择性对比图;
图3是微波制备的20Ni/CaO-10CeO2-W催化剂在反应温度550℃的稳定性图。
具体实施方式
下面通过实施例对本发明作进一步详细说明,但本发明保护范围不局限于所述内容。
实施例1:制备1g 20Ni/CaO-10CeO2催化剂(20表示催化剂中Ni百分含量为20%,10表示催化剂中CeO2百分含量为10%,后面同上)
(1)称取硝酸镍0.9909g、硝酸钙2.9519g、硝酸铈0.2523g至烧杯中,加入12mL去离子水搅拌混合均匀后,称取3.4649g柠檬酸加入搅拌至完全溶解;将混合液置于80℃下水浴加热4.5h,得到湿凝胶;将湿凝胶放在微波马弗炉中,以10℃/min的升温速率升温至800℃,在微波下煅烧30min,以10℃/min降温速率降温至室温,得到催化剂20Ni/CaO-10CeO2;
(2)使用 20Ni/CaO-10CeO2催化剂催化制备氢气
A、反应在固定床反应器中进行,催化剂用量200mg,水和乙醇摩尔比为6:1,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,流速为18.85mL/min,GHSV=12990h-1,比较本实施例20Ni/CaO-10CeO2催化剂和20Ni/CaO-10CeO2催化剂(传统煅烧法)在反应温度为450℃、500℃、550℃、600℃、650℃、700℃下的反应活性;氢气选择性=氢气摩尔流量/(氢气摩尔流量+含碳化合物摩尔流量);
结果见图1、2,在相同的实验条件下,两种催化剂均能在450℃就实现乙醇100%转化,其中本实施例20Ni/CaO-10CeO2催化剂在节约80%制备时间、节省成本的情况下,氢气选择性优于传统煅烧法制备的20Ni/CaO-10CeO2催化剂。
B、稳定性测试是在催化剂用量200mg,水醇比6:1,乙醇水溶液流速0.02mL/min,GHSV=12990h-1,反应温度550℃的条件下进行的;在线反应200h,乙醇的转化率一直保持100%,氢气选择性虽然有些波动,但是基本上保持在70%左右,结果如图3。
实施例2:制备1g 16Ni/CaO-10CeO2催化剂
(1)称取硝酸镍0.7928g、硝酸钙3.1206g、硝酸铈0.2523g至烧杯中,加入12mL去离子水搅拌混合均匀后,称取3.4703g柠檬酸加入搅拌至完全溶解;将混合液置于75℃下水浴加热5h,得到湿凝胶;将湿凝胶放在微波马弗炉中,以10℃/min的升温速率升温至810℃,在微波下煅烧40min,以10℃/min降温速率降温至室温,得到催化剂16Ni/CaO-10CeO2;
(2)使用 16Ni/CaO-10CeO2催化剂催化制备氢气
反应在固定床反应器中进行,催化剂用量200mg,水和乙醇摩尔比为6:1,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,流速为18.85mL/min,GHSV=12990h-1,考察16Ni/CaO-10CeO2催化剂在反应温度为450℃、500℃、550℃、600℃、650℃、700℃下的反应活性;结果表明,16Ni/CaO-10CeO2-W催化剂的催化性能较好,450℃乙醇转化率就能达到100%,并且随着反应温度的提高,氢气选择性一直呈上升的趋势,700℃达到最大。
实施例3:制备1g 12Ni/CaO-12CeO2催化剂
(1)称取硝酸镍0.5947g、硝酸钙3.2046g、硝酸铈0.3027g至烧杯中,加入13mL去离子水搅拌混合均匀后,称取3.4278g柠檬酸加入搅拌至完全溶解;将混合液置于85℃下水浴加热4h,得到湿凝胶;将湿凝胶放在微波马弗炉中,以10℃/min的升温速率升温至820℃,在微波下煅烧50min,以10℃/min降温速率降温至室温,得到催化剂12Ni/CaO-12CeO2;
(2)使用 12Ni/CaO-12CeO2催化剂催化制备氢气
反应在固定床反应器中进行,催化剂用量200mg,水和乙醇摩尔比为6:1,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,流速为18.85mL/min,GHSV=12990h-1,考察8Ni/CaO-10CeO2催化剂在反应温度为450℃、500℃、550℃、600℃、650℃、700℃下的反应活性;结果表明,催化剂450℃就实现了乙醇的100%转化,氢气选择性650℃达到最大值69%。
实施例4:制备1g 20Ni/CaO-10La2O3催化剂
(1)称取硝酸镍0.9909g、硝酸钙2.9519g、硝酸镧0.2658g至烧杯中,加入12mL去离子水搅拌混合均匀后,称取3.4718g柠檬酸加入搅拌至完全溶解;将混合液置于85℃下水浴加热5h,得到湿凝胶;将湿凝胶放在微波马弗炉中,以10℃/min的升温速率升温至800℃,在微波下煅烧50min,以10℃/min降温速率降温至室温,得到催化剂20Ni/CaO-10La2O3;
(2)使用 20Ni/CaO-10La2O3催化剂催化制备氢气
乙醇水蒸气重整反应在固定床反应器中进行,催化剂用量200mg,水和乙醇摩尔比为6:1,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,流速为18.85mL/min,GHSV=12990h-1,考察了微波制备的20Ni/CaO-10CeO2催化剂和20Ni/CaO-10La2O3催化剂分别在反应温度为450℃、500℃、550℃、600℃、650℃、700℃反应活性。结果表明;20Ni/CaO-10La2O3催化剂在450℃同样就实现了乙醇的100%转化,氢气选择性随着反应温度一直上升,550℃达到最大值69.92%。
实施例5:制备1g 20Ni/CaO-14CeO2催化剂
(1)称取硝酸镍0.9909g、硝酸钙2.7832g、硝酸铈0.3531g至烧杯中,加入12mL去离子水搅拌混合均匀后,称取3.3636g柠檬酸加入搅拌至完全溶解;将混合液置于75℃下水浴加热5h,得到湿凝胶;将湿凝胶放在微波马弗炉中,以10℃/min的升温速率升温至810℃,在微波下煅烧40min,以10℃/min降温速率降温至室温,得到催化剂20Ni/CaO-14CeO2;
(2)使用 20Ni/CaO-14CeO2催化剂催化制备氢气
反应在固定床反应器中进行,催化剂用量200mg,水和乙醇摩尔比为6:1,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,流速为18.85mL/min,GHSV=12990h-1,考察20Ni/CaO-14CeO2催化剂在反应温度为450℃、500℃、550℃、600℃、650℃、700℃下的反应活性;结果表明,20Ni/CaO-14CeO2催化剂的乙醇转化率和氢气选择性均较好,450℃乙醇就完全转化,氢气选择性450℃达到65.77%,从反应温度500℃开始一直保持在70%以上,600℃达到最大值73.62%。
Claims (4)
1.一种Ni基催化剂的制备方法,其特征在于,包括以下步骤:
(1)将硝酸铈或硝酸镧、硝酸钙、硝酸镍加入去离子水中,搅拌至完全溶解,然后将柠檬酸添加到上述混合溶液中,搅拌至完全溶解;
(2)将步骤(1)溶液置于75-85℃下水浴加热4-5h,得到湿凝胶;
(3)将步骤(2)湿凝胶置于微波马弗炉中在微波、800-850℃下煅烧30-60min,降温至室温后取出,制得Ni基催化剂Ni/CaO-CeO2或Ni/CaO-La2O3,其中Ni的含量为8-20%,CeO2或La2O3含量为5-15%,CaO含量为87-65%。
2.根据权利要求1所述的Ni基催化剂的制备方法,其特征在于:硝酸镍与柠檬酸的质量比为1:3.4-9.5。
3.根据权利要求1所述的Ni基催化剂的制备方法,其特征在于:步骤(3)升温速率为10℃/min,降温速率为10℃/min。
4.权利要求1-3中任一项所述的Ni基催化剂的制备方法制得的Ni基催化剂在氢气制备中的应用,其特征在于:以乙醇、水为原料,以Ni基催化剂为催化剂,将乙醇水溶液气化后通入到装有催化剂的固定床反应器中,在450-700℃、0.3MPa下制得氢气。
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