CN110639523A - 一种耐硫中毒的Ni基甲烷化催化剂及其制备方法和应用 - Google Patents
一种耐硫中毒的Ni基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 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 title abstract description 13
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- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
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- 230000004913 activation Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
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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 description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
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- 230000000052 comparative effect Effects 0.000 description 5
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Abstract
本发明公开了一种耐硫中毒的Ni基甲烷化催化剂及其制备方法和应用。所述Ni基甲烷化催化剂以金属Ni粒子为活性组分,以SiO2为载体,其中金属Ni粒子的质量百分含量为8‑12%;所述SiO2载体的比表面积不低于650m2g‑1,孔径不低于20nm,孔容不小于4cm3g‑1,其中内表面积所占比例不低于90%;所述金属Ni粒子粒径为6‑9nm,并且Ni粒子分布在载体孔道内部。本发明提供了所述催化剂在合成气甲烷化中的应用。本发明所述Ni基甲烷化催化剂,相比于传统的将Ni活性中心负载于载体外表面的催化剂,具有更好的耐硫中毒性能,故其具有更长的使用寿命。
Description
(一)技术领域
本发明涉及一种Ni基甲烷化催化剂及其制备方法和在合成气甲烷化(CO+3H2-CH4+H2O)中的应用。
(二)背景技术
随着对环境和大气污染问题的日益重视,对清洁能源的需求与日俱增。天然气作为一种污染小、效率高的能源,近年来的市场需求迅速上升。由于我国“富煤、平油、少气”的能源结构特点,以煤或生物质为原料经气化过程首先得到合成气(CO+H2),然后再通过催化反应过程得到CH4是获得该种清洁能源的重要途径之一。根据大量文献报道,Ru、Rh、Fe、Co、Ni等金属都具有一定的甲烷化反应活性。相比较而言,金属Ni基催化剂由于具有较高的活性和低廉的价格,是目前最具工业应用潜力的甲烷化催化剂。但是,由于煤制合成气中不可避免地存在少量的含硫杂质(例如:H2S),从而导致Ni基甲烷化催化剂发生硫中毒而引发失活。通过添加各种碱金属、贵金属助剂可以改变Ni活性中心的性质,这是目前常用于提高Ni基催化剂耐硫中毒性能的主要方法。
(三)发明内容
本发明要解决的技术问题是提供一种具有耐硫中毒性能的Ni基甲烷化催化剂及其制备方法和在合成气甲烷化中的应用。
为解决上述技术问题,本发明采用如下技术方案:
一方面,本发明提供了一种Ni基甲烷化催化剂,该催化剂以金属Ni粒子为活性组分,以SiO2为载体,其中金属Ni粒子的质量百分含量为8-12%;所述SiO2载体的比表面积不低于650m2g-1,孔径不低于20nm,孔容不小于4cm3g-1,其中内表面积所占比例不低于90%;所述金属Ni粒子粒径为6-9nm,并且Ni粒子分布在载体孔道内部。
进一步,金属Ni粒子的质量百分含量为10%。
另一方面,本发明提供了一种所述Ni基甲烷化催化剂的制备方法,所述制备方法为:
1)将一定量的含镍无机盐溶解于一定体积的乙醇中得到溶液A;
2)按照负载量要求将溶液A滴加至SiO2固体颗粒上;
3)将步骤2)所得样品去除溶剂,然后将所得固体颗粒在空气中于400-600℃焙烧3-6h,得到负载有NiO前驱体粒子的催化剂前驱体,所述NiO前驱体粒子的粒径在6-8nm;
4)将步骤3)所得催化剂前驱体在含氢气气氛下还原活化,活化温度为400-500℃,活化时间为4-10h,即得到Ni基甲烷化催化剂。
进一步,所述步骤1)中,含镍无机盐是硝酸镍六水合物;其中硝酸镍的浓度为0.03-0.05g cm-3。
进一步,所述步骤3)中,去除溶剂的温度为50-100℃。
进一步,所述步骤3)中,焙烧在空气气氛下,温度为500℃,时间为4h。
进一步,所述步骤4)中,含氢气气氛中氢气的体积百分含量为5-100%,若除氢气外还有其他气体,则其他气体可以是N2或Ar。
进一步,所述步骤4)中,活化温度为480℃,活化时间为5h。
第三方面,本发明提供了所述Ni基甲烷化催化剂在合成气(CO+H2)甲烷化中的应用。
与现有技术比较,本发明具有以下优点:
(1)本发明所制得的Ni基甲烷化催化剂中金属Ni粒子粒径为6-9nm,并且Ni粒子分布在载体孔道内部。在甲烷化反应过程中,由于含硫气体分子的扩散速度要低于H2和CO分子,所以孔内Ni粒子表面的含硫分子浓度要低于位于载体外表面的Ni粒子表面的含硫分子浓度,利用气体分子孔内扩散性能的差异来降低活性中心表面H2S浓度,提高Ni基甲烷化催化剂的耐硫中毒性能;故其相比于传统的将Ni活性中心负载于载体外表面的催化剂,具有更长的使用寿命。
(2)本发明所述催化剂的制备方法过程及所用设备简单,实现了将Ni活性中心负载于载体孔道内的目的。
(四)附图说明
图1是实施例1所使用的SiO2-A载体的低温N2物理吸附-脱附图。
图2是比较例1所使用的SiO2-P载体的低温N2物理吸附-脱附图。
图3是实施例1和比较例1所制备的催化剂在甲烷化反应中的耐硫中毒性能测试结果图。
(五)具体实施方式
下面以具体实施例对本发明的技术方案做进一步说明,但本发明的保护范围不受下列实施例的限制。同时,在不背离本发明精神的前提下,可以对所举实施例的形式和细节进行各种省略、替换和变化。
实施例1:
将称得的0.2745g六水合硝酸镍加入到7cm3乙醇中形成溶液。然后,将该溶液逐滴滴加至0.5g SiO2-A载体(纳诺科技)上。在65℃条件下干燥12h后可得到固体样品。将此干燥后的固体样品在500℃空气气氛下焙烧4h得到催化剂前驱体。最后,在氢气气氛下,将所制备的SiO2负载型Ni基催化剂在480℃条件下还原5h以得到最终催化剂(Ni/SiO2-A,金属Ni负载量=10%wt.)。图1是实施例1所使用的SiO2-A载体的低温N2物理吸附-脱附图。从图中可以发现,该样品在P/P0接近1时,N2吸附量突然大幅增加并且没有出现平台。这表明该样品主要存在孔径较大的孔结构(表1)。同时,该样品几乎不存在外表面。在另一方面,由实施例1所述方法制备的催化剂的NiO粒径要小于催化剂的孔径(表1)。综上所述,经还原处理后的Ni/SiO2-A催化剂的金属Ni粒子应位于SiO2载体的介孔孔道内。
比较例1:
将2.7459g六水合硝酸镍和2.9264g聚乙二醇加入到150cm3去离子水和50cm3正丁醇溶液中,然后将此混合液在120℃回流2h,接着加入5g SiO2-P载体(青岛白沙河催化剂厂生产)(图2),在120℃条件下去除溶剂。再将所得的样品在400℃空气气氛下焙烧5h。最后将焙烧后的样品在氢气气氛下经过480℃还原活化5h得到Ni/SiO2-P催化剂(金属Ni的负载量为10%wt.)。图2是比较例1所使用的SiO2-P载体的低温N2物理吸附-脱附图。与图1相比,该样品在P/P0接近1时N2吸附量没有出现大幅增加现象,并且出现了一个平台区。
实施例2:甲烷化反应性能测试
由实施例1和比较例1所制备的催化剂,采用固定床反应器对其在甲烷化反应中的耐硫中毒性能进行评价测试。反应原料气组成:CO:23%,N2:8%,H2S:20ppm,H2余量;原料气流量:60cm3min-1;压力:1MPa;反应温度:420℃。原料气中N2做为内标,通过气相色谱对气相产物进行在线定性和定量分析。从实验数据中(图3)可以发现,由实施例1制备的Ni/SiO2-A催化剂在含有H2S分子的CO甲烷化反应过程中,其CO转化率在15h内能保持在~100%。而按比较例1所制备的Ni/SiO2-P催化剂在相同反应条件和反应时间内,其CO转化率快速下降到约19%左右,发生了明显失活现象。因此,由本发明专利报道的方法制备的催化剂在CO甲烷化反应中具有更好的耐硫中毒性能。
表1.Ni/SiO2-A和Ni/SiO2-P催化剂的性质表征结果:
Claims (9)
1.一种Ni基甲烷化催化剂,该催化剂以金属Ni粒子为活性组分,以SiO2为载体,其中金属Ni粒子的质量百分含量为8-12%;所述SiO2载体的比表面积不低于650m2g-1,孔径不低于20nm,孔容不小于4cm3g-1,其中内表面积所占比例不低于90%;所述金属Ni粒子粒径为6-9nm,并且Ni粒子分布在载体孔道内部。
2.如权利要求1所述的Ni基甲烷化催化剂,其特征在于:金属Ni粒子的质量百分含量为10%。
3.一种如权利要求1所述的Ni基甲烷化催化剂的制备方法,所述制备方法为:
1)将一定量的含镍无机盐溶解于一定体积的乙醇中得到溶液A;
2)按照负载量要求将溶液A滴加至SiO2固体颗粒上;
3)将步骤2)所得样品去除溶剂,然后将所得固体颗粒在空气中于400-600℃焙烧3-6h,得到负载有NiO前驱体粒子的催化剂前驱体,所述NiO前驱体粒子的粒径在6-8nm之间;
4)将步骤3)所得催化剂前驱体在含氢气气氛下还原活化,活化温度为400-500℃,活化时间为4-10h,即得到Ni基甲烷化催化剂。
4.如权利要求3所述的制备方法,其特征在于:所述步骤1)中,含镍无机盐是硝酸镍六水合物;溶液A中硝酸镍的浓度为0.03-0.05g cm-3。
5.如权利要求3所述的制备方法,其特征在于:所述步骤3)中,去除溶剂的温度为50-100℃。
6.如权利要求3所述的制备方法,其特征在于:所述步骤3)中,焙烧温度为500℃,焙烧时间为4h。
7.如权利要求3所述的制备方法,其特征在于:所述步骤4)中,含氢气气氛中氢气的体积百分含量为5-100%,若含氢气气氛中除氢气外还含有其他气体,则其他气体是N2或Ar。
8.如权利要求3所述的制备方法,其特征在于:所述步骤4)中,活化温度为480℃,活化时间为5h。
9.如权利要求1所述的Ni基甲烷化催化剂在合成气甲烷化中的应用。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4132672A (en) * | 1976-03-15 | 1979-01-02 | American Gas Association | Methanation catalyst |
US4490480A (en) * | 1982-04-23 | 1984-12-25 | Internationale Octrooi Maatschappij "Octropa"B.V. | Nickel catalyst on alumina support |
EP0974637A1 (en) * | 1998-07-22 | 2000-01-26 | Engelhard Corporation | Hydrogenation process |
CN105170159A (zh) * | 2015-04-17 | 2015-12-23 | 浙江工业大学 | 一种负载型Ni基催化剂及其应用 |
CN105377422A (zh) * | 2013-03-28 | 2016-03-02 | 新加坡科技研究局 | 甲烷化催化剂 |
CN107199047A (zh) * | 2016-03-17 | 2017-09-26 | 华东理工大学 | 一种分散于sba-15孔道内的镍基甲烷化催化剂及其制备和应用 |
CN107519911A (zh) * | 2016-06-21 | 2017-12-29 | 华东理工大学 | 一种利用有机小分子添加剂制备镍基催化剂及其在甲烷化反应中的应用 |
-
2018
- 2018-06-26 CN CN201810672429.3A patent/CN110639523A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4132672A (en) * | 1976-03-15 | 1979-01-02 | American Gas Association | Methanation catalyst |
US4490480A (en) * | 1982-04-23 | 1984-12-25 | Internationale Octrooi Maatschappij "Octropa"B.V. | Nickel catalyst on alumina support |
EP0974637A1 (en) * | 1998-07-22 | 2000-01-26 | Engelhard Corporation | Hydrogenation process |
CN105377422A (zh) * | 2013-03-28 | 2016-03-02 | 新加坡科技研究局 | 甲烷化催化剂 |
CN105170159A (zh) * | 2015-04-17 | 2015-12-23 | 浙江工业大学 | 一种负载型Ni基催化剂及其应用 |
CN107199047A (zh) * | 2016-03-17 | 2017-09-26 | 华东理工大学 | 一种分散于sba-15孔道内的镍基甲烷化催化剂及其制备和应用 |
CN107519911A (zh) * | 2016-06-21 | 2017-12-29 | 华东理工大学 | 一种利用有机小分子添加剂制备镍基催化剂及其在甲烷化反应中的应用 |
Non-Patent Citations (6)
Title |
---|
CHANGKUN YUAN: "The SiO2 supported bimetallic Ni–Ru particles: A good sulfur-tolerant catalyst for methanation reaction", 《CHEMICAL ENGINEERING JOURNAL》 * |
JING WANG ET.AL: "Deposition of carbon species on the surface of metal: As a poison or a promoter for the long-term stability of Ni/SiO2 methanation catalyst?", 《CHEMI CAL ENGIN EERING JOURNAL》 * |
W.D. FITZHARRIS ET.AL: "Sulfur Deactivation of Nickel Methanation Catalysts", 《JOURNAL OF CATALYSIS》 * |
张蕾著: "《烟气脱硫脱硝技术及催化剂的研究进展》", 31 July 2016, 中国矿业大学出版社 * |
王晶,姚楠: "适用于合成气制甲烷的Ni基催化剂", 《化学进展》 * |
袁涌天等: "载体孔结构对镍基甲烷化催化剂催化活性的影响", 《天气化工(C1化学与化工)》 * |
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