CN112588292A - 一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用 - Google Patents
一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000004964 aerogel Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 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 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical group O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000001476 alcoholic effect Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000000352 supercritical drying Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 13
- 239000003245 coal Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
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- 230000002431 foraging effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 230000006378 damage Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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Abstract
本发明提供一种以TiO2气凝胶为载体的甲烷化催化剂以及制备方法和应用,其包含:以金属单质计占催化剂总重量的3~60%的活性组分Ni,以氧化物计占催化剂总重量的2~30%的第一助剂,以氧化物计占催化剂总重量的0.5~30%的第二助剂和余量的载体TiO2气凝胶,其中,所述第一助剂选自La2O3、CeO2、Pr2O3和Sm2O3中的一种或多种,所述第二助剂选自Fe2O3、Cr2O3、Co3O4、CuO、ZnO、MoO3、ZrO2、MgO、CaO、SrO和BaO中的一种或多种。本发明提供的甲烷化催化剂低温活性得到改善,具有良好热稳定性,适合应用于CO/CO2甲烷化反应过程。
Description
技术领域
本发明属于煤制天然气技术领域,具体涉及一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用。所述甲烷化催化剂适用于CO/CO2甲烷化反应,属于催化剂化学以及煤基合成天然气新型煤化工能源领域。
背景技术
随着我国经济发展,社会生活水平提高,环境保护成为社会发展的重要课题,市场对清洁能源的需求越来越大。基于我国“富煤、贫油、少气”的资源禀赋,我国天然气对外依赖度超过50%。在此背景下,发展煤基合成天然气生产技术和产业一方面填补传统天然气市场的供应缺口,同时提供了一种优化的煤炭资源清洁、高效利用的技术和途径。
国外以Topsoe和Johnson Matthey等公司为代表,应用沉淀法或者均相沉淀法研发了生产合成天然气甲烷化催化剂产品,如专利US3988262和US3988263。近年随着我国煤基合成天然气产业发展,完全甲烷化催化剂也成为国内研究的热点,专利CN101716513A应用均相沉淀法制备了稀土基完全甲烷化催化剂,可用于高温至650℃的甲烷化反应过程,但均相沉淀中采用氨的缓释剂有可能产生稳定的镍氨络合物,使得金属镍发生了流失。专利CN102091631A应用多次浸渍法制备了甲烷化催化剂用于合成天然气生产过程,但浸渍法制备的甲烷化催化剂有可能存在高温条件下稳定性不足的现象。
尽管国内外、尤其是国内已有不同方法制备的生产合成天然气的完全甲烷化催化剂技术报导,但是目前以TiO2气凝胶作为载体制备甲烷化催化剂的方式未见报道。气凝胶是指通过溶胶凝胶法,用一定的干燥方式使气体取代凝胶中的液相而形成的一种多孔固态材料。本发明的发明人经过深入研究发现,以固体TiO2作为载体的甲烷化催化剂所需活性组分少,低温活性得到改善,缺点是其比表面积小,而气凝胶态TiO2作为载体解决了比表面积小的问题,而且提高了催化剂热稳定性。
发明内容
因此,本发明的目的在于提供一种以TiO2气凝胶为载体的甲烷化催化剂及其制备方法和应用。
本发明的上述目的是通过如下技术方案实现的。
一方面,本发明提供了一种以TiO2气凝胶为载体的甲烷化催化剂,其包含:以金属单质计占催化剂总重量的3~60%的活性组分Ni,以氧化物计占催化剂总重量的2~30%的第一助剂,以氧化物计占催化剂总重量的0.5~30%的第二助剂和余量的载体TiO2气凝胶,其中,所述第一助剂选自La2O3、CeO2、Pr2O3和Sm2O3中的一种或多种,所述第二助剂选自Fe2O3、Cr2O3、Co3O4、CuO、ZnO、MoO3、ZrO2、MgO、CaO、SrO和BaO中的一种或多种。
另一方面,本发明还提供了所述以TiO2气凝胶为载体的甲烷化催化剂的制备方法,该制备方法包括以下步骤:
(1)将钛酸四丁酯、无水乙醇和水混合均匀,用盐酸调节pH值至1~5,静置后用氨水调节pH值至6~10,静置老化后用无水乙醇洗涤,经超临界干燥获得TiO2气凝胶载体;
(2)将活性组分的前驱物、第一助剂的前驱物和第二助剂的前驱物混合后溶于无水乙醇中,制得醇溶液。
(3)将步骤(1)所得TiO2气凝胶载体浸泡在步骤(2)配制的醇溶液中,加热搅拌4~48小时后用无水乙醇洗涤,烘干,焙烧,获得氧化态催化剂;
(4)将氧化态催化剂在H2或H2/N2混合气中还原,获得预还原态催化剂。
根据本发明提供的制备方法,其中,步骤(1)中钛酸四丁酯、无水乙醇和去离子水的摩尔比可以为1:5~20:1~5,优选为1:8~15:2~4。
根据本发明提供的制备方法,其中,步骤(2)中制备所述醇溶液的过程中,相对于1000克无水乙醇,所述活性组分的前驱物的用量以Ni单质计可以为20~60克;所述第一助剂的前驱物的用量以氧化物计可以为10~25克;所述第二助剂的前驱物的用量以氧化物计可以为10~35克。
在本发明的一种优选的实施方案中,步骤(2)中制备所述醇溶液的温度为30~80℃。
在本发明的一种优选的实施方案中,步骤(3)中的焙烧温度为600~850℃。
在本发明的一种优选的实施方案中,步骤(4)中的还原温度为500~650℃。
根据本发明提供的制备方法,其中,步骤(4)中所述H2/N2混合气中H2含量大于30体积%。
根据本发明提供的制备方法,其中,步骤(4)中的还原条件可以包括:还原气体积空速800~4000h-1,以0.5~1℃/min的速率升温至500~600℃,并在该温度下保持4~8h。
在本发明的一种优选的实施方案中,所述步骤(4)还包括:还原结束后在还原气氛中冷却至常温,随后缓慢通入空气,至系统没有温升。
再一方面,本发明还提供了所述的甲烷化催化剂或者由本发明的制备方法制得的甲烷化催化剂在CO和/或CO2甲烷化反应中的应用。
本发明提供的甲烷化催化剂低温活性得到改善,具有良好热稳定性,适合应用于CO/CO2甲烷化反应过程。
具体实施方式
下面结合具体实施方式对本发明进行进一步的详细描述,给出的实施例仅为了阐明本发明,而不是为了限制本发明的范围。
实施例1
(1)将110ml无水乙醇和8ml去离子水混合均匀,滴入钛酸四丁酯48.4956g,超声混合均匀,形成溶胶,用盐酸调节溶胶的pH值到2。静置一定时间后,用氨水调节溶胶的pH值到8,静置老化一定时间,使用无水乙醇洗涤6次,置换溶胶中水分,经超临界干燥获得TiO2气凝胶载体。
(2)称取40.1318克Ni(NO3)2·6H2O、5.5209克La(NO3)3·6H2O、10.3014克Zr(NO3)4·5H2O、3.4161克Ca(NO3)2·4H2O溶解于60℃的300ml无水乙醇中制得醇溶液。
(3)将步骤一所得TiO2气凝胶载体浸泡在步骤二配置的醇溶液中,加热搅拌24h,随后用无水乙醇洗涤6次,在60℃的鼓风烘箱中烘干2h,随后将烘箱温度以1℃/min的速率升至110℃,保持12h,将所得产品放入马弗炉,以1℃/min的速率升温至650℃焙烧4h,得到氧化态催化剂。
(4)将氧化态催化剂在H2中进行还原,具体的还原条件为:还原体积空速2000h-1,以1℃/min的速率升温至550℃,并在该温度下保持6h,还原结束后在还原气氛中冷却至常温,随后缓慢通入空气,至系统没有温升,获得预还原态催化剂。
实施例2
(1)将100ml无水乙醇和15ml去离子水混合均匀,滴入钛酸四丁酯68.0293g,超声混合均匀,形成溶胶,用盐酸调节溶胶的pH值到3.5。静置一定时间后,用氨水调节溶胶的pH值到9,静置老化一定时间,使用无水乙醇洗涤6次,置换溶胶中水分,经超临界干燥获得TiO2气凝胶载体。
(2)称取43.1853克Ni(NO3)2·6H2O、11.8981克Zr(NO3)4·5H2O和4.5093克Ca(NO3)2·4H2O溶解于50℃的300ml的无水乙醇中制得醇溶液。
(3)将步骤一所得TiO2气凝胶载体浸泡在步骤二配置的醇溶液中,加热搅拌24h,随后用无水乙醇洗涤6次,在60℃的鼓风烘箱中烘干2h,随后将烘箱温度以1℃/min的速率升至110℃,保持12h,将所得产品放入马弗炉,以1℃/min的速率升温至600℃焙烧6h,得到氧化态催化剂。
(4)将氧化态催化剂在H2/N2体积比2:3的气体中进行还原,具体的还原条件为:还原体积空速5000h-1,以1℃/min的速率升温至550℃,并在该温度下保持5h,还原结束后在还原气氛中冷却至常温,随后缓慢通入空气,至系统没有温升,获得预还原态催化剂。
实施例3
(1)将170ml无水乙醇和10ml去离子水混合均匀,滴入钛酸四丁酯74.8322g,超声混合均匀,形成溶胶,用盐酸调节溶胶的pH值到2.5。静置一定时间后,用氨水调节溶胶的pH值到7,静置老化一定时间,使用无水乙醇洗涤6次,置换溶胶中水分,经超临界干燥获得TiO2气凝胶作为载体。
(2)称取58.8599克Ni(NO3)2·6H2O、8.1183克Ce(NO3)3·6H2O、15.1087克Zr(NO3)4·5H2O和5.4376克Mg(NO3)2·6H2O溶解于70℃的300ml无水乙醇中,制得醇溶液。
(3)将步骤一所得TiO2气凝胶载体浸泡在步骤二配置的醇溶液中,加热搅拌24h,随后用去无水乙醇洗涤6次,在60℃的鼓风烘箱中烘干2h,随后将烘箱温度以1℃/min的速率升至110℃,保持12h,将所得产品放入马弗炉,以1℃/min的速率升温至700℃焙烧5h,得到氧化态催化剂。
(4)将氧化态催化剂在H2/N2体积比3:1的气体中进行还原,具体的还原条件为:还原体积空速3000h-1,以1℃/min的速率升温至550℃,并在该温度下保持4h,还原结束后在还原气氛中冷却至常温,随后缓慢通入空气,至系统没有温升,获得预还原态催化剂。
对比例1
(1)称取53.5078克Ni(NO3)2·6H2O、7.3614克La(NO3)3·6H2O、13.7348克Zr(NO3)4·5H2O、71.2745克Al(NO3)3·9H2O和4.5546克Ca(NO3)2·4H2O溶解于60℃的300ml去离子水中,得溶液1。
称取57.2712克Na2CO3和16.0196克NaHCO3,溶解于60℃的300ml去离子水中,得溶液2。
(2)将溶液1缓慢加入溶液2中,搅拌1h形成沉淀,沉淀静置1h。
(3)用60℃去离子水将步骤(2)得到的沉淀洗涤6次,过滤,在110℃的鼓风烘箱中将滤渣烘干12h,再以1℃/min的速率加热至500℃焙烧6h后成型得到沉淀法氧化态催化剂。
(4)将氧化态催化剂在H2/N2体积比3:1的气体中进行还原,具体的还原条件为:还原体积空速3000h-1,以1℃/min的速率升温至550℃,并在该温度下保持4h,还原结束后在还原气氛中冷却至常温,随后缓慢通入空气,至系统没有温升,获得预还原态催化剂。
催化剂活性评价
在煤气化经甲烷化生产合成天然气的高温和低温反应条件下评价催化剂活性,具体考察催化剂上CO和CO2的转化率。其中高温甲烷化反应条件列于表1,低温甲烷化反应条件列于表2。
表1
表2
催化剂耐高温性能评价
采用高温水热老化条件对催化剂预先进行破坏实验,考察经过破坏实验后催化剂床层热点位置移动情况,以判断和比较催化剂的稳定性。高温水热老化条件列于表3。
表3
实施例和对比例制得的催化剂的性能对比数据列于表4
表4
通过表4中的数据可以看出,与沉淀法催化剂(对比例1)相比,使用本方法制备的实施例1-3的催化剂的低温活性得到改善,具有良好热稳定性。
Claims (10)
1.一种以TiO2气凝胶为载体的甲烷化催化剂,其包含:以金属单质计占催化剂总重量的3~60%的活性组分Ni,以氧化物计占催化剂总重量的2~30%的第一助剂,以氧化物计占催化剂总重量的0.5~30%的第二助剂和余量的载体TiO2气凝胶,其中,所述第一助剂选自La2O3、CeO2、Pr2O3和Sm2O3中的一种或多种,所述第二助剂选自Fe2O3、Cr2O3、Co3O4、CuO、ZnO、MoO3、ZrO2、MgO、CaO、SrO和BaO中的一种或多种。
2.权利要求1所述以TiO2气凝胶为载体的甲烷化催化剂的制备方法,该制备方法包括以下步骤:
(1)将钛酸四丁酯、无水乙醇和水混合均匀,用盐酸调节pH值至1~5,静置后用氨水调节pH值至6~10,静置老化后用无水乙醇洗涤,经超临界干燥获得TiO2气凝胶载体;
(2)将活性组分的前驱物、第一助剂的前驱物和第二助剂的前驱物混合后溶于无水乙醇中,制得醇溶液。
(3)将步骤(1)所得TiO2气凝胶载体浸泡在步骤(2)配制的醇溶液中,加热搅拌4~48小时后用无水乙醇洗涤,烘干,焙烧,获得氧化态催化剂;
(4)将氧化态催化剂在H2或H2/N2混合气中还原,获得预还原态催化剂。
3.根据权利要求2所述的制备方法,其中,步骤(1)中钛酸四丁酯、无水乙醇和去离子水的摩尔比为1:5~20:1~5,优选为1:8~15:2~4。
4.根据权利要求2所述的制备方法,其中,步骤(2)中制备所述醇溶液的过程中,相对于1000克无水乙醇,所述活性组分的前驱物的用量以Ni单质计为20~60克;所述第一助剂的前驱物的用量以氧化物计为10~25克;所述第二助剂的前驱物的用量以氧化物计为10~35克。
5.根据权利要求2所述的制备方法,其中,步骤(2)中制备所述醇溶液的温度为30~80℃。
6.根据权利要求2所述的制备方法,其中,步骤(3)中的焙烧温度为600~850℃。
7.根据权利要求2所述的制备方法,其中,步骤(4)中的还原温度为500~650℃。
8.根据权利要求2所述的制备方法,其中,步骤(4)中所述H2/N2混合气中H2含量大于30体积%。
9.根据权利要求2所述的制备方法,其中,步骤(4)中的还原条件包括:还原气体积空速800~4000h-1,以0.5~1℃/min的速率升温至500~600℃,并在该温度下保持4~8h。
10.权利要求1所述的甲烷化催化剂或者由权利要求2至9中任一项所述的制备方法制得的甲烷化催化剂在CO和/或CO2甲烷化反应中的应用。
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