CN103920496B - 介孔材料包覆式钴基费托合成催化剂及其制备方法 - Google Patents
介孔材料包覆式钴基费托合成催化剂及其制备方法 Download PDFInfo
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- CN103920496B CN103920496B CN201410162615.4A CN201410162615A CN103920496B CN 103920496 B CN103920496 B CN 103920496B CN 201410162615 A CN201410162615 A CN 201410162615A CN 103920496 B CN103920496 B CN 103920496B
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- mesoporous material
- tropsch synthesis
- based fischer
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 193
- 239000013335 mesoporous material Substances 0.000 title claims abstract description 108
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011148 porous material Substances 0.000 claims abstract description 44
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
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- 239000003960 organic solvent Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
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- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
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- 230000000694 effects Effects 0.000 description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 8
- 229910052622 kaolinite Inorganic materials 0.000 description 8
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 239000002028 Biomass Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
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Abstract
本发明公开了一种介孔材料包覆式钴基费托合成催化剂及其制备方法。该催化剂包括二氧化硅载体,二氧化硅载体表面负载有活性组分钴和选择性助剂锆,活性组分钴和选择性助剂锆外面包覆有介孔材料壳层。其制备方法包括:制取负载锆的二氧化硅载体;以该载体为基础制得初始钴基费托合成催化剂;配制介孔材料前驱溶液;通过浸渍、晶化、洗涤、干燥和焙烧,获得介孔材料包覆式钴基费托合成催化剂。本发明通过介孔材料壳层包裹保护催化剂活性成分,壳层厚度可控,使用寿命长,反应活性较高,稳定性好,介孔材料的孔道结构提供了可供CO和H2扩散的通道,C5 +选择性高、甲烷选择性低。特别适用于鼓泡浆态床反应器或者连续搅拌浆态床反应器。
Description
技术领域
本发明属于工业催化费托合成领域,具体地指一种介孔材料包覆式钴基费托合成催化剂及其制备方法。
背景技术
煤、石油和天然气是人类文明赖以生存和发展的重要能源基础,是一个国家经济可持续发展和安全稳定的保障。随着人类的不断开采,人类将面临严重的能源危机,所以寻找可再生的新能源是科学家们急需解决的问题。我国是一个农业大国,拥有大量的可再生的各种生物质,将可再生的生物能源代替化石能源将是解决能源危机的重要途径。
将生物质气化制合成气,再将合成气(CO+H2)在催化剂的作用下转变成碳氢化合物(—CH2—)的过程称作费托合成反应(FTS)。将生物质转化成合成气再经费托合成生产各种油品能够有效地解决能源危机。
费托合成的基本反应为:CO+2H2→(—CH2—)+H2O。由这个反应式我们可以看到产物水是伴随着碳氢化合物一起产生的,而且在某些反应器中,比如浆态床反应器中,由于后混合,水的浓度会达到很高。目前应用最广泛的工业化的费托催化剂活性物种主要是铁和钴。对于钴基催化的费托合成反应,催化剂活性物种为金属钴,很可能被重量占总产物50%的产物水氧化,从而使催化剂失活,而且CO的转化率越高,失活越严重。例如,Bertole等(J.Catal.,2002,210:84-96)报道水会造成非负载钴基催化剂的失活,因为高的水分压(>0.4MPa)极易造成催化剂的烧结,从而减小了钴的比表面,导致金属位活性的降低或催化剂表面CO吸附量的减少。Batholomew(Appl.Catal.A,2001,212.17-60)也认为水蒸汽可以增加负载型催化剂的烧结速率。由于钴基催化剂的成本相对较高,因此催化剂的稳定性、活性和选择性要求都会比较高,制备对水不敏感的催化剂就显得非常有必要。
中国专利CN101203304A中公开了一种氧化载体负载钴基催化剂,该氧化载体包括铝和0.01~20%的锂,其中锂主要是以铝酸锂的形式存在,这种含铝酸锂的载体具有改善的耐水性,并且减少铝酸钴的形成,该催化剂具有高活性和高C5 +的选择性。但是该载体的制备方法苛刻,需要在700~1000℃的高温下长时间煅烧。
中国专利CN1785515A报道了一种用合成气合成中间馏分油的催化剂,该催化剂以介孔二氧化锆为载体,该催化剂金属钴的含量为5~35wt%,贵金属含量0~2wt%,非贵金属氧化物0~10wt%,该催化剂具有活性高,稳定性好,C11~C20烃的选择性高以及良好的机械性能,但是载体介孔氧化锆的制备方法复杂,成本高。
发明内容
本发明的目的就是要克服现有技术所存在的不足,提供一种寿命长、稳定性好、壳层厚度可控的介孔材料包覆式钴基费托合成催化剂及其制备方法。
为实现上述目的,本发明所提供的介孔材料包覆式钴基费托合成催化剂,包括二氧化硅载体,其特殊之处在于:所述二氧化硅载体表面负载有活性组分钴和选择性助剂锆,所述活性组分钴和选择性助剂锆外面包覆有介孔材料壳层。
本发明的催化剂是先将活性组分通过浸渍法负载在二氧化硅载体表面,然后在活性组分外面包覆具有规整孔道的介孔材料,介孔材料的壳层厚度可通过改变参数加以控制。所述介孔材料壳层的厚度设计为1.8~13μm,优选的厚度为2.0~6.0μm。这样,介孔材料壳层将活性成分包覆在孔道内部,避免了活性成分的团聚和脱落,同时介孔材料的规整孔道提供了CO和H2的传质通道,保证了催化剂的高反应活性。
为了防止催化剂在反应过程中或运输转移过程中由于活性组分脱落而减少催化剂的活性,避免活性金属Co被反应过程中生成的水氧化而失活,所述介孔材料壳层外面还覆盖有疏水性有机化合物层。
本发明中,所述二氧化硅载体采用无机硅胶。
优选地,所述无机硅胶的比表面积为150~350m2/g、平均孔径为3~50nm、孔容为0.7~1.7mL/g、粒径为20~200μm。
最佳地,所述无机硅胶的比表面积为200~300m2/g、平均孔径为8~13nm、孔容为0.75~1.3mL/g、粒径40~150μm。
本发明中,所述活性组分钴的含量占催化剂总重量的10~25%,所述选择性助剂锆的含量占催化剂总重量的5~10%。
优选地,所述活性组分钴的含量占催化剂总重量的15~20%,所述选择性助剂锆的含量占催化剂总重量的5~8%。
最佳地,所述活性组分钴的含量占催化剂总重量的20~25%,所述选择性助剂锆的含量占催化剂总重量的8~10%。
本发明中,所述催化剂的比表面积为150~400m2/g,平均孔径为2~40nm,孔容为0.5~1.4mL/g。
进一步地,所述催化剂的比表面积为250~350m2/g,平均孔径为3~9nm、孔容为0.6~1.0mL/g。
上述介孔材料包覆式钴基费托合成催化剂的制备方法,包括以下步骤:
1)将二氧化硅载体浸渍在锆盐的水溶液中,陈化12~24h后,在70~120℃下干燥8~24h,再在400~500℃下焙烧3~12h,获得负载锆的二氧化硅载体;
2)将所得负载锆的二氧化硅载体浸渍在钴盐的水溶液中,陈化12~24h后,在70~120℃下干燥8~24h,再在400~500℃下焙烧3~12h,获得初始钴基费托合成催化剂;
3)将模板剂P123溶解到硝酸溶液中,搅拌使其混合均匀,再加入正硅酸乙酯,继续搅拌12~30h,获得介孔材料前驱溶液;
4)将所得初始钴基费托合成催化剂浸渍在所得介孔材料前驱溶液中,然后进行晶化、洗涤、干燥和焙烧,即可获得介孔材料包覆式钴基费托合成催化剂。
进一步地,它还包括如下步骤:
5)将所得介孔材料包覆式钴基费托合成催化剂浸渍在疏水性有机溶液中,密封3~12h后取出,再选择清洗用有机溶剂漂洗干净,最后在60~90℃条件下干燥3~8h,即可获得疏水性介孔材料包覆式钴基费托合成催化剂。
进一步地,所述步骤1)中,锆盐为硝酸锆或硝酸氧锆中的一种,优选硝酸氧锆。
进一步地,所述步骤2)中,钴盐为碳酸钴或硝酸钴中的一种,优选硝酸钴。
进一步地,所述步骤3)中,硝酸溶液的浓度为1~2mol/L,搅拌温度为25~45℃,搅拌至溶液变澄清,再加入正硅酸乙酯,继续搅拌12~24h,获得介孔材料前驱溶液。
所述模板剂P123采用已知的三嵌段共聚物,全称为聚氧乙烯-聚氧丙烯-聚氧乙烯,其分子式为PEO-PPO-PEO,其通式为EO20PO70EO20。
更进一步地,所述步骤4)中,晶化条件为温度80~130℃、时间20~100h、转速7~20r/min;洗涤条件为去离子水洗涤至中性;干燥条件为80~120℃干燥10~20h;焙烧条件为400~550℃保持5~12h。
优选地,晶化条件为温度90~120℃、时间30~80h、转速7~15r/min。
更进一步地,所述步骤5)中,疏水性有机溶液为聚甲基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷或三甲基氯硅烷中的一种。
更进一步地,所述步骤5)中,清洗用有机溶剂为正己烷、丙酮或乙醇中的一种。
再进一步地,所述步骤5)中,所得介孔材料包覆式钴基费托合成催化剂浸渍在疏水性有机溶液中的密封时间为3~8h,再选择清洗用有机溶剂漂洗2~3次。
本发明的有益效果在于:所研制的钴基费托合成催化剂,打破了传统的钴基催化剂和蛋壳型催化剂的局限性,通过先将介孔材料壳层包裹在催化剂的表面,壳层厚度可通过工艺参数控制,在保护了催化剂活性成分的同时,介孔材料的孔道结构提供了可供CO和H2扩散的通道。进一步地,在介孔材料壳层上引入超疏水有机分子,可有效地将水分子阻挡在通道之外。
这样,不仅避免了反应过程中由于催化剂的磨损或者催化剂在活化和转移过程中活性组分的脱落,而且防止了反应过程中水蒸汽对催化剂的影响,从而大幅提高了催化剂的稳定性,有效地延长了催化剂的使用寿命,具有良好的工业应用前景。本发明的Co基催化剂具有使用寿命长、反应活性高、稳定性好、C5 +选择性高、甲烷选择性低的特点,特别适于鼓泡浆态床反应器或者连续搅拌浆态床反应器。
附图说明
图1为本发明催化剂的制备工艺流程示意图。
图2为本发明催化剂B的壳层厚度TEM照片显微结构示意图。
图3为本发明催化剂C的壳层厚度TEM照片显微结构示意图。
图4为本发明催化剂D的壳层厚度TEM照片显微结构示意图。
图5为本发明催化剂E的壳层厚度TEM照片显微结构示意图。
图6为本发明催化剂F的壳层厚度TEM照片显微结构示意图。
图7为本发明催化剂G的壳层厚度TEM照片显微结构示意图。
具体实施方式
为了更好地解释本发明,以下结合附图和具体实施例对本发明作进一步的详细说明,但它们不对本发明构成限定。
实施例1:制备催化剂B
催化剂B的组成包括无机硅胶载体、活性组分Co、助剂Zr和介孔材料壳层。Zr元素的含量为5wt%,Co元素的含量为20wt%。
催化剂B的制备方法如下:
1)将30g比表面积280m2/g、孔容1.25mL/g、平均孔径13.6nm、粒径40μm的无机硅胶载体浸渍在45mL含5.07g的ZrO(NO3)2的水溶液中,空气中陈化16h后,将其放置于110℃下干燥8h,再于马弗炉中450℃下焙烧10h,获得负载锆的无机硅胶载体;
2)将负载锆的无机硅胶载体浸渍在63mL含39.43g的Co(NO3)3·6H2O的水溶液中,空气中陈化16h,将其放置于110℃下干燥8h,再在马弗炉中450℃下焙烧10h,获得初始钴基费托合成催化剂;
3)将4g模板剂P123加入到140mL的2mol/L的硝酸溶液中溶解,35℃下搅拌至溶液变澄清,再加入8.4g正硅酸乙脂,继续搅拌24h后,获得介孔材料前驱溶液;
4)将介孔材料前驱溶液转移到干净的聚四氟反应釜内,取初始钴基费托合成催化剂10g浸渍在介孔材料前驱溶液中,然后固定在水热合成装置中,在130℃下晶化20h,转速为7rpm/min;取出用去离子水洗涤至中性,在100℃下干燥12h,550℃下焙烧5h,即可获得介孔材料包覆式钴基费托合成催化剂B。
经检测,所得催化剂B的比表面积为291m2/g,孔容1.16mL/g,平均孔径10.6nm,壳层厚度较薄,厚度为1.8μm,催化剂B的壳层厚度TEM照片如图2所示。
实施例2:制备催化剂C
催化剂C的组成包括无机硅胶载体、活性组分Co、助剂Zr和和实施例1所述的介孔材料壳层。Zr元素的含量为5wt%,Co元素的含量为20wt%。
催化剂C的制备方法与实施例1基本相同,所不同的是晶化时间60h代替实施例1中步骤3)的晶化时间。
经检测,所得催化剂C的比表面积为301m2/g,孔容0.98mL/g,平均孔径9.5nm,壳层厚度较厚,厚度为5μm。催化剂C的壳层厚度TEM照片如图3所示。
实施例3:制备催化剂D
催化剂D的组成包括无机硅胶载体、活性组分Co、助剂Zr和实施例1所述的介孔材料结构的壳层。Zr元素的含量为5wt%,Co元素的含量为20wt%。催化剂的比表面积为320m2/g,孔容1.02mL/g,平均孔径8.9nm,壳层厚度为13μm。
催化剂D的制备方法与实施例1基本相同,所不同的是晶化时间100h代替实施例1中步骤3)的晶化时间。催化剂D的壳层厚度TEM照片如图4所示。
实施例4:制备催化剂E
催化剂E的组成包括无机硅胶载体、活性组分Co、助剂Zr、介孔材料壳层以及三甲基氯硅烷疏水性有机化合物层。Zr元素的含量为5wt%,Co元素的含量为20wt%。
催化剂E的制备方法如下:
1)将30g比表面积280m2/g、孔容1.25mL/g、平均孔径13.6nm、粒径40μm的无机硅胶载体浸渍在45mL含5.07g的ZrO(NO3)2的水溶液中,空气中陈化16h后,将其放置于110℃下干燥8h,再于马弗炉中450℃下焙烧10h,获得负载锆的无机硅胶载体;
2)将负载锆的无机硅胶载体浸渍在63mL含39.43g的Co(NO3)3·6H2O的水溶液中,空气中陈化16h,将其放置于110℃下干燥8h,再在马弗炉中450℃下焙烧10h,获得初始钴基费托合成催化剂;
3)介孔材料壳层的包覆:将4g模板剂P123加入到140mL的2mol/L的硝酸溶液中溶解,35℃下搅拌至澄清,再加入8.4g正硅酸乙脂,继续搅拌24h后,获得介孔材料前驱溶液;
4)将介孔材料前驱溶液转移到干净的聚四氟反应釜内,取初始钴基费托合成催化剂10g浸渍在介孔材料前驱溶液中,然后固定在水热合成装置中,在130℃下晶化20h,转速为7rpm/min;取出催化剂用去离子水洗涤至中性,在100℃下干燥12h,550℃下焙烧5h,获得介孔材料包覆式钴基费托合成催化剂;
5)将所得介孔材料包覆式钴基费托合成催化剂浸渍在200mL的三甲基氯硅烷溶液中,密封浸渍8h后取出,再用无水乙醇漂洗2次,最后在80℃下干燥8h,即可获得疏水性介孔材料包覆式钴基费托合成催化剂E。
经检测,所得催化剂E的比表面积为279m2/g,孔容0.86mL/g,平均孔径8.2nm,壳层厚度为2.5μm,催化剂E的壳层厚度TEM照片如图5所示。
实施例5:制备催化剂F
催化剂F的组成包括无机硅胶载体、活性组分Co、助剂Zr、介孔材料壳层以及聚甲基三乙氧基硅烷疏水性有机化合物层。Zr元素的含量为5wt%,Co元素的含量为20wt%。
催化剂F的制备方法与实施例4基本相同,所不同的是用聚甲基三乙氧基硅烷代替实施例4中的三甲基氯硅烷。
经检测,催化剂F的比表面积为282m2/g,孔容0.91mL/g,平均孔径7.9nm,壳层厚度为2.1μm,催化剂F的壳层厚度TEM照片如图6所示。
实施例6:制备催化剂G
催化剂G的组成包括无机硅胶载体、活性组分Co、助剂Zr、介孔材料壳层以及γ-氨丙基三乙氧基硅烷疏水性有机化合物层。Zr元素的含量为5wt%,Co元素的含量为20wt%。
催化剂G的制备方法与实施例4基本相同,所不同的是用γ-氨丙基三乙氧基硅烷代替实施例4中的三甲基氯硅烷。
经检测,催化剂G的比表面积为280m2/g,孔容0.83mL/g,平均孔径8.5nm,壳层厚度为2.3μm,催化剂G的壳层厚度TEM照片如图7所示。
实施例7:制备催化剂H
催化剂H的组成包括无机硅胶载体、活性组分Co、助剂Zr、介孔材料壳层以及γ-氨丙基三乙氧基硅烷疏水性有机化合物层。Zr元素的含量为8wt%,Co元素的含量为25wt%。
催化剂H的制备方法如下:
1)将30g比表面150m2/g、孔容1.3mL/g、平均孔径8nm、平均粒径90μm的无机硅胶载体浸渍在45mL含16.74g的Zr(NO3)4·5H2O的水溶液中,空气中陈化24h后,将其放置于120℃下干燥10h,再于马弗炉中500℃下焙烧3h,获得负载锆的无机硅胶载体;
2)将负载锆的无机硅胶载体浸渍在63mL含22.5g的CoCO3的水溶液中,空气中陈化24h,将其放置于120℃下干燥10h,再在马弗炉中500℃下焙烧3h,获得初始钴基费托合成催化剂;
3)介孔材料壳层的包覆:将4g模板剂P123加入到140mL的1mol/L的硝酸溶液中溶解,45℃下搅拌至澄清,再加入8.4g正硅酸乙脂,继续搅拌12h后,获得介孔材料前驱溶液;
4)将介孔材料前驱溶液转移到干净的聚四氟反应釜内,取初始钴基费托合成催化剂10g浸渍在介孔材料前驱溶液中,然后固定在水热合成装置中,在100℃下晶化24h,转速为10rpm/min;取出催化剂用去离子水洗涤至中性,在80℃下干燥20h,400℃下焙烧12h,获得介孔材料包覆式钴基费托合成催化剂;
5)将所得介孔材料包覆式钴基费托合成催化剂浸渍在200mL的γ-氨丙基三乙氧基硅烷溶液中,密封浸渍3h后取出,并用正己烷漂洗3次,再在60℃下干燥3h,即可获得疏水性介孔材料包覆式钴基费托合成催化剂H。
经检测,催化剂H的比表面积为200m2/g,孔容1.0mL/g,平均孔径4.0nm,壳层厚度为2.0μm。
实施例8:制备催化剂I
催化剂I的组成包括无机硅胶载体、活性组分Co、助剂Zr、介孔材料壳层以及γ-氨丙基三乙氧基硅烷疏水性有机化合物层。Zr元素的含量为10wt%,Co元素的含量为10wt%。
催化剂I的制备方法如下:
1)将30g比表面300m2/g、孔容0.75mL/g、平均孔径13nm,平均粒径150μm的无机硅胶载体浸渍在45mL含9.5g硝酸氧锆的水溶液中,空气中陈化12h后,将其放置于70℃下干燥24h,再于马弗炉中400℃下焙烧12h,获得负载锆的无机硅胶载体;
2)将负载锆的无机硅胶载体浸渍在63mL含7.55g的CoCO3的水溶液中,空气中陈化12h,将其放置于70℃下干燥24h,再在马弗炉中400℃下焙烧12h,获得初始钴基费托合成催化剂;
3)介孔材料壳层的包覆:将4g模板剂P123加入到140mL的2mol/L的硝酸溶液中溶解,25℃下搅拌至澄清,再加入8.4g正硅酸乙脂,继续搅拌30h后,获得介孔材料前驱溶液;
4)将介孔材料前驱溶液转移到干净的聚四氟反应釜内,取初始钴基费托合成催化剂10g浸渍在介孔材料前驱溶液中,然后固定在水热合成装置中,在80℃下晶化70h,转速为15rpm/min;取出催化剂用蒸馏水洗涤至中性,在120℃下干燥10h,500℃下焙烧8h,获得介孔材料包覆式钴基费托合成催化剂;
5)将所得介孔材料包覆式钴基费托合成催化剂浸渍在200mL的γ-氨丙基三乙氧基硅烷溶液中,密封浸渍15h后取出,再用丙酮漂洗2次,然后在90℃下干燥5h,即可获得疏水性介孔材料包覆式钴基费托合成催化剂I。
经检测,催化剂I的比表面积为350m2/g,孔容0.6mL/g,平均孔径9nm,壳层厚度为6μm。
对比例1:传统催化剂A
传统催化剂A的组成包括无机硅胶载体、活性组分Co、助剂Zr。Zr元素的含量为5wt%,Co元素的含量为20wt%。
催化剂A的制备方法如下:
1)将30g比表面积280m2/g、孔容1.25mL/g、平均孔径13.6nm、粒径40μm的无机硅胶载体浸渍在45mL含5.07g的ZrO(NO3)2的水溶液中,空气中陈化16h后,将其放置于110℃下干燥8h,再于马弗炉中450℃下焙烧10h,获得负载锆的无机硅胶载体;
2)将负载锆的无机硅胶载体浸渍在63mL含39.43g的Co(NO3)3·6H2O的水溶液中,空气中陈化16h,将其放置于110℃下干燥8h,再在马弗炉中450℃下焙烧10h,得到钴基费托合成催化剂A。
上述各实施例所制得催化剂B~I与对比例所制得传统催化剂A用于生物质制合成气合成液态烃的评价结果参见下面的表1。
由表1可以看出在传统催化剂上包裹一层介孔材料壳层后,CO的转化率变化不大,均在55~65%之间,主要是因为虽然介孔材料的壳层有一定的厚度,但是催化剂的粒径较小,传质阻力也比较小,而且介孔材料壳层为H2和CO提供了传质通道。而液态烃的选择性会稍微有所增大,甲烷的选择性会稍微降低,可能是由于介孔材料的壳层能够避免活性组分在活化和转移过程中因摩擦而脱落。另外,介孔材料壳层能够阻挡体相的水分直接接触活性中心。当在壳层表面进行疏水性有机修饰后,液态烃的选择性会增大,甲烷的选择性也明显下降很多,说明在介孔材料壳层引入疏水性物质后,能有效地防止催化剂被水氧化而失活,当小分子的水分一旦生成即被合成气顺着疏水性有机化合物层吹到壳层外面。由此可见,本发明制备所得的Co基催化剂具有较高的反应活性,C5 +选择性高,甲烷选择性低。
特别是在介孔材料壳层上面引入疏水性物质后,液态烃的选择性提高得更大,由于修饰催化剂F的有机物分子结构比较小,疏水性表现得比催化剂E、G要稍微差一点。修饰催化剂E的有机物价格要比修饰催化剂G的贵,而且易挥发,腐蚀性大。催化剂H的比表面积和孔径较小,其活性和液态烃的选择性会稍有降低,催化剂I的粒径较大,壳层较厚,存在一定的传质阻力,CO的转化率下降了,而催化剂I的晶化时间较长,故催化剂G要优于催化剂E、F、H、I。
表1催化剂A~I的活性及选择性对比
催化剂 | XCO/% | S(CH4)/% | S(C2-C4)% | S(C5 +)/% | S(CO2)/% |
A | 60.3 | 14.5 | 7.1 | 76.9 | 1.5 |
B | 61.0 | 10.6 | 7.1 | 81.1 | 1.2 |
C | 60.5 | 10.2 | 7.5 | 81.0 | 1.3 |
D | 60.0 | 10.7 | 7.0 | 80.9 | 1.4 |
E | 62.4 | 5.5 | 6.3 | 87.2 | 1.0 |
F | 63.1 | 9.2 | 6.9 | 82.9 | 1.0 |
G | 64.5 | 5.2 | 6.3 | 87.5 | 0.9 |
H | 60.0 | 7.6 | 7.1 | 84.3 | 1.0 |
I | 55.3 | 7.8 | 7.5 | 83.8 | 0.9 |
为了更好地说明本发明的优点,申请人对传统催化剂A和本发明催化剂B、G进行了长周期稳定性研究,其结果列于下面的表2和表3中。
表2催化剂在长时间运转下CO的转化率对比
催化剂 | t=500h | t=800h | t=1000h | t=1500h | t=2000h | t=2500h |
A | 60.3% | 58.6% | 50.4% | 40.3% | 31.8% | 25.8% |
B | 61.0% | 60.9% | 59.9% | 56.9% | 50.2% | 40.1% |
G | 64.5% | 64.4% | 64.3% | 63.9% | 62.2% | 60.1% |
表3催化剂在长时间运转下液态烃(C5+)的选择性对比
催化剂 | t=500h | t=800h | t=1000h | t=1500h | t=2000h | t=2500h |
A | 76.9% | 76.8% | 71.3% | 63.5% | 58.1% | 53.5% |
B | 81.0% | 81.1% | 79.5% | 76.4% | 70.6% | 67.8% |
G | 87.4% | 87.5% | 87.5% | 86.5% | 85.9% | 84.9% |
由表2和表3可以看出未经任何修饰的传统催化剂A反应时间达到800h活性就开始下降,可能是由于催化剂在长时间的搅拌状态下表面的金属Co会因摩擦而从催化剂表面脱落,而且反应生成的水会使催化剂被氧化而失活。而介孔材料壳层包覆形成催化剂B、G后,其反应时间延长到1500h,CO的转化率仍然在55%以上,可能是催化剂的壳层能够保护催化剂的活性中心,防止催化剂的金属部分因摩擦而脱落。特别是经过疏水性有机物修饰的催化剂G,当反应2500h时,其催化活性依然很高,CO的转化率仍然在60%左右,液态烃的选择性在85%左右,说明催化剂的寿命明显延长,这是由于在介孔材料壳层上引入疏水基后能够有效的防止催化剂的金属部分脱落,还能有效地避免水分与活性中心接触而使催化剂失活。由此可见,本发明制备的Co基催化剂具有极好的稳定性,并且有效提高了使用寿命。
Claims (22)
1.一种介孔材料包覆式钴基费托合成催化剂,包括二氧化硅载体,其特征在于:所述二氧化硅载体表面负载有活性组分钴和选择性助剂锆,所述活性组分钴和选择性助剂锆外面包覆有介孔材料壳层;所述介孔材料包覆式钴基费托合成催化剂按照以下步骤制备:
1)将二氧化硅载体浸渍在锆盐的水溶液中,陈化12~24h后,在70~120℃下干燥8~24h,再在400~500℃下焙烧3~12h,获得负载锆的二氧化硅载体;
2)将所得负载锆的二氧化硅载体浸渍在钴盐的水溶液中,陈化12~24h后,在70~120℃下干燥8~24h,再在400~500℃下焙烧3~12h,获得初始钴基费托合成催化剂;
3)将模板剂P123溶解到硝酸溶液中,搅拌使其混合均匀,再加入正硅酸乙酯,继续搅拌12~30h,获得介孔材料前驱溶液;
4)将所得初始钴基费托合成催化剂浸渍在所得介孔材料前驱溶液中,然后进行晶化、洗涤、干燥和焙烧,即可获得介孔材料包覆式钴基费托合成催化剂。
2.根据权利要求1所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述介孔材料壳层外面还覆盖有疏水性有机化合物层。
3.根据权利要求1或2所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述二氧化硅载体为无机硅胶。
4.根据权利要求3所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述无机硅胶的比表面积为150~350m2/g、平均孔径为3~50nm、孔容为0.7~1.7mL/g、粒径为20~200μm。
5.根据权利要求4所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述无机硅胶的比表面积为200~300m2/g、平均孔径为8~13nm、孔容为0.75~1.3mL/g、粒径40~150μm。
6.根据权利要求1或2所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述活性组分钴的含量占催化剂总重量的10~25%,所述选择性助剂锆的含量占催化剂总重量的5~10%。
7.根据权利要求6所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述活性组分钴的含量占催化剂总重量的15~20%,所述选择性助剂锆的含量占催化剂总重量的5~8%。
8.根据权利要求6所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述活性组分钴的含量占催化剂总重量的20~25%,所述选择性助剂锆的含量占催化剂总重量的8~10%。
9.根据权利要求1或2所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述介孔材料壳层的厚度为1.8~13μm。
10.根据权利要求9所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述介孔材料壳层的厚度为2.0~6.0μm。
11.根据权利要求1或2所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述催化剂的比表面积为150~400m2/g,平均孔径为2~40nm,孔容为0.5~1.4mL/g。
12.根据权利要求11所述的介孔材料包覆式钴基费托合成催化剂,其特征在于:所述催化剂的比表面积为250~350m2/g,平均孔径为3~9nm、孔容为0.6~1.0mL/g。
13.一种根据权利要求1所述的介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于,它包括以下步骤:
1)将二氧化硅载体浸渍在锆盐的水溶液中,陈化12~24h后,在70~120℃下干燥8~24h,再在400~500℃下焙烧3~12h,获得负载锆的二氧化硅载体;
2)将所得负载锆的二氧化硅载体浸渍在钴盐的水溶液中,陈化12~24h后,在70~120℃下干燥8~24h,再在400~500℃下焙烧3~12h,获得初始钴基费托合成催化剂;
3)将模板剂P123溶解到硝酸溶液中,搅拌使其混合均匀,再加入正硅酸乙酯,继续搅拌12~30h,获得介孔材料前驱溶液;
4)将所得初始钴基费托合成催化剂浸渍在所得介孔材料前驱溶液中,然后进行晶化、洗涤、干燥和焙烧,即可获得介孔材料包覆式钴基费托合成催化剂。
14.根据权利要求13所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:它还包括如下步骤:
5)将所得介孔材料包覆式钴基费托合成催化剂浸渍在疏水性有机溶液中,密封3~12h后取出,再选择清洗用有机溶剂漂洗干净,最后在60~90℃条件下干燥3~8h,即可获得疏水性介孔材料包覆式钴基费托合成催化剂。
15.根据权利要求13或14所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤1)中,锆盐为硝酸锆或硝酸氧锆中的一种。
16.根据权利要求13或14所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤2)中,所述钴盐为碳酸钴或硝酸钴中的一种。
17.根据权利要求13或14所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤3)中,硝酸溶液的浓度为1~2mol/L,搅拌温度为25~45℃,搅拌至溶液变澄清,再加入正硅酸乙酯,继续搅拌12~24h,获得介孔材料前驱溶液。
18.根据权利要求13或14所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤4)中,晶化条件为温度80~130℃、时间20~100h、转速7~20r/min;洗涤条件为去离子水洗涤至中性;干燥条件为80~120℃干燥10~20h;焙烧条件为400~550℃保持5~12h。
19.根据权利要求18所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤4)中,晶化条件为温度90~120℃、时间30~80h、转速7~15r/min。
20.根据权利要求14所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤5)中,疏水性有机溶液为聚甲基三乙氧基硅烷、γ-氨丙基三乙氧基硅烷或三甲基氯硅烷中的一种。
21.根据权利要求14所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤5)中,清洗用有机溶剂为正己烷、丙酮或乙醇中的一种。
22.根据权利要求20所述介孔材料包覆式钴基费托合成催化剂的制备方法,其特征在于:所述步骤5)中,所得介孔材料包覆式钴基费托合成催化剂浸渍在疏水性有机溶液中的密封时间为3~8h,再选择清洗用有机溶剂漂洗2~3次。
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CN201410162615.4A CN103920496B (zh) | 2014-04-22 | 2014-04-22 | 介孔材料包覆式钴基费托合成催化剂及其制备方法 |
EP15783307.0A EP3135372A4 (en) | 2014-04-22 | 2015-02-06 | Cobalt-based fischer-tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor |
RU2016145414A RU2642451C1 (ru) | 2014-04-22 | 2015-02-06 | Катализатор синтеза фишера-тропша на основе кобальта, покрытый мезопористыми материалами, и способ его получения |
PCT/CN2015/072402 WO2015161701A1 (zh) | 2014-04-22 | 2015-02-06 | 介孔材料包覆式钴基费托合成催化剂及其制备方法 |
AU2015251403A AU2015251403A1 (en) | 2014-04-22 | 2015-02-06 | Cobalt-based Fischer-Tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor |
JP2016563174A JP6337144B2 (ja) | 2014-04-22 | 2015-02-06 | メソ多孔性材料被覆型コバルト系フィッシャートロプシュ合成触媒及びその調製方法 |
CA2946638A CA2946638A1 (en) | 2014-04-22 | 2015-02-06 | Cobalt-based fischer-tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor |
KR1020167032475A KR101906027B1 (ko) | 2014-04-22 | 2015-02-06 | 메조포러스 물질로 코팅된 코발트계 피셔-트롭시 합성 촉매제 및 그 제조 방법 |
US15/331,925 US10363550B2 (en) | 2014-04-22 | 2016-10-24 | Mesoporous material-coated cobalt-based catalyst for fischer-tropsch synthesis and method for preparing the same |
AU2018205112A AU2018205112C1 (en) | 2014-04-22 | 2018-07-11 | Cobalt-based Fischer-Tropsch synthesis catalyst coated with mesoporous materials and preparation method therefor |
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CN103920496B (zh) * | 2014-04-22 | 2015-11-18 | 武汉凯迪工程技术研究总院有限公司 | 介孔材料包覆式钴基费托合成催化剂及其制备方法 |
CN104162430A (zh) * | 2014-09-09 | 2014-11-26 | 安徽工程大学 | 一种蛋壳型的催化剂 |
CN104368344B (zh) * | 2014-10-09 | 2016-09-14 | 武汉凯迪工程技术研究总院有限公司 | 钴基费托合成催化剂及其制备方法和应用 |
CN104289231B (zh) * | 2014-10-09 | 2017-02-08 | 武汉凯迪工程技术研究总院有限公司 | 高分散度钴基费托合成催化剂及其制备方法和应用 |
US10066169B2 (en) * | 2015-07-14 | 2018-09-04 | Research & Business Foundation Sungkyunkwan University | Mesoporous cobalt-metal oxide catalyst for Fischer-Tropsch synthesis reactions and a preparing method thereof |
CN107262093B (zh) * | 2017-06-23 | 2019-07-26 | 福州大学 | 一种甲烷催化燃烧催化剂及其制备方法 |
CN109718774B (zh) * | 2017-10-27 | 2022-02-08 | 中国石油化工股份有限公司 | 一种催化剂及其制备方法和应用及费托合成方法 |
CN110614115A (zh) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | 载体为球形三介孔复合材料的异丁烷脱氢催化剂及其制备方法和应用 |
RU2679801C1 (ru) * | 2018-10-31 | 2019-02-13 | Общество с ограниченной ответственностью "Объединенный центр исследований и разработок" (ООО "РН-ЦИР") | Катализатор для получения синтетических легких олефинов C2-C4 из синтез-газа и способ его получения |
CN112973694A (zh) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | 一种铝元素促进的无序介孔二氧化硅负载的钴基催化剂及其制备与应用 |
CN113754798A (zh) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | 类球形超大孔介孔材料和聚烯烃催化剂及其制备方法以及烯烃聚合方法 |
CN112391191B (zh) * | 2020-10-30 | 2022-09-02 | 山西潞安煤基清洁能源有限责任公司 | 一种防止费托合成工艺中催化剂凝结结垢的方法以及催化剂和应用 |
CN112354534B (zh) * | 2020-11-04 | 2023-01-13 | 万华化学集团股份有限公司 | 一种催化剂的制备方法及其在杨梅醛合成中的应用 |
CN115090283B (zh) * | 2022-07-25 | 2024-01-02 | 浙江新化化工股份有限公司 | 一种负载型核壳催化剂、其制备方法及其在催化环戊基丁内酯加氢中应用 |
CN115337930B (zh) * | 2022-08-19 | 2024-03-15 | 常州大学 | 一种石墨化碳改性壳-核Co基催化剂的制备方法及在一氧化碳加氢催化中的应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1522178A (zh) * | 2001-05-08 | 2004-08-18 | �յ�-��ѧ��˾ | 用于费-托合成过程的高表面积、小晶粒尺寸催化剂 |
CN101505867A (zh) * | 2006-08-25 | 2009-08-12 | 新日铁工程技术株式会社 | 从合成气体制造烃的催化剂、催化剂的制造方法、催化剂的再生方法以及从合成气体制造烃的方法 |
CN101811050A (zh) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | 一种有机疏水改性钴基费托合成催化剂及制备和应用 |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DZ2724A1 (fr) * | 1998-02-20 | 2003-09-01 | Sasol Tech Pty Ltd | Procédé pour la production d'hydrocarbures à partir d'un gaz de synthèse et leurs catalyseurs. |
US6930219B2 (en) * | 1999-09-07 | 2005-08-16 | Abb Lummus Global Inc. | Mesoporous material with active metals |
US7005118B2 (en) * | 2002-07-25 | 2006-02-28 | Instituto Mexicano Del Petroleo | Synthetic mesoporous material with radially assembled nanotubes |
US7285329B2 (en) * | 2004-02-18 | 2007-10-23 | Hitachi Metals, Ltd. | Fine composite metal particles and their production method, micro-bodies, and magnetic beads |
DE102005019103B4 (de) * | 2004-04-26 | 2023-09-21 | Sasol Technology (Proprietary) Ltd. | Verfahren zur Herstellung eines auf Cobalt basierenden Katalysators für die Fischer-Tropsch-Synthese und Verfahren zur Herstellung eines Fischer-Tropsch-Kohlenwasserstoffproduktes |
US7566678B2 (en) * | 2005-02-17 | 2009-07-28 | Bp Exploration Operating Company Limited | Modified catalyst and use of this catalyst for the conversion of synthesis gas to hydrocarbons |
CN101426725B (zh) * | 2006-04-20 | 2011-04-13 | 旭硝子株式会社 | 核壳型二氧化硅及其制造方法 |
JP4808688B2 (ja) * | 2006-08-25 | 2011-11-02 | 新日本製鐵株式会社 | 合成ガスから炭化水素を製造する触媒、触媒の製造方法、触媒の再生方法、及び合成ガスから炭化水素を製造する方法 |
BRPI0705939A2 (pt) * | 2007-10-29 | 2009-06-23 | Petroleo Brasileiro Sa | processo para a produção de catalisadores hìbridos para a sìntese de fischer-tropsch e catalisador hìbrido produzido de acordo com o processo |
US8216961B2 (en) * | 2008-08-27 | 2012-07-10 | Korea University Research And Business Foundation | Nanoparticles including metal oxide having catalytic activity |
US20110250122A1 (en) * | 2008-11-07 | 2011-10-13 | The Regents Of The University Of California | Core-Shell Nanocatalyst For High Temperature Reactions |
GB0905222D0 (en) * | 2009-03-26 | 2009-05-13 | Johnson Matthey Plc | Method for producing a supported metal nitrate |
JP5603063B2 (ja) * | 2009-12-21 | 2014-10-08 | 花王株式会社 | 複合シリカ粒子の製造方法 |
JP4807536B2 (ja) * | 2010-01-07 | 2011-11-02 | 独立行政法人日本原子力研究開発機構 | 水素燃焼触媒及びその製造方法並びに水素燃焼方法 |
KR101230625B1 (ko) * | 2010-05-06 | 2013-02-06 | 한국과학기술연구원 | 메조포러스 실리카 구조체를 이용한 피셔-트롭시 공정용 촉매 |
JP2012100778A (ja) * | 2010-11-08 | 2012-05-31 | Universal Entertainment Corp | ゲーミングマシン |
CN102078818B (zh) * | 2010-12-27 | 2015-04-08 | 中南民族大学 | 以sba-16分子筛为载体的催化剂及其制法和应用 |
EP2530125A1 (en) * | 2011-05-30 | 2012-12-05 | Total SA | Core-shell particles with catalytic activity |
BR112014015648B1 (pt) * | 2011-12-14 | 2020-09-15 | Sasol Technology (Proprietary) Limited | Método de preparação de um suporte de catalisador modificado, método de preparação de um precursor do catalisador, método de preparo de um catalisador, processo de síntese de hidrocarbonetos e produtos |
EP2626131A1 (en) * | 2012-02-08 | 2013-08-14 | Studiengesellschaft Kohle mbH | Highly sinter-stable metal nanoparticles supported on mesoporous graphitic particles and their use |
CN102728359B (zh) * | 2012-06-28 | 2014-10-01 | 中南民族大学 | 一种以氧化硅介孔泡沫为载体的钴基催化剂及应用 |
CN102836706B (zh) * | 2012-09-12 | 2015-05-06 | 中国石油天然气股份有限公司 | 高温热稳定的钯复合催化剂及其制备方法与应用 |
US9827554B2 (en) * | 2012-09-21 | 2017-11-28 | Jx Nippon Oil & Energy Corporation | Fischer-tropsch synthesis catalyst, method for producing same, and method for producing hydrocarbon |
CN103920496B (zh) * | 2014-04-22 | 2015-11-18 | 武汉凯迪工程技术研究总院有限公司 | 介孔材料包覆式钴基费托合成催化剂及其制备方法 |
-
2014
- 2014-04-22 CN CN201410162615.4A patent/CN103920496B/zh active Active
-
2015
- 2015-02-06 WO PCT/CN2015/072402 patent/WO2015161701A1/zh active Application Filing
- 2015-02-06 JP JP2016563174A patent/JP6337144B2/ja active Active
- 2015-02-06 AU AU2015251403A patent/AU2015251403A1/en not_active Abandoned
- 2015-02-06 RU RU2016145414A patent/RU2642451C1/ru not_active IP Right Cessation
- 2015-02-06 KR KR1020167032475A patent/KR101906027B1/ko active IP Right Grant
- 2015-02-06 CA CA2946638A patent/CA2946638A1/en not_active Abandoned
- 2015-02-06 EP EP15783307.0A patent/EP3135372A4/en not_active Withdrawn
-
2016
- 2016-10-24 US US15/331,925 patent/US10363550B2/en active Active
-
2018
- 2018-07-11 AU AU2018205112A patent/AU2018205112C1/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1522178A (zh) * | 2001-05-08 | 2004-08-18 | �յ�-��ѧ��˾ | 用于费-托合成过程的高表面积、小晶粒尺寸催化剂 |
CN101505867A (zh) * | 2006-08-25 | 2009-08-12 | 新日铁工程技术株式会社 | 从合成气体制造烃的催化剂、催化剂的制造方法、催化剂的再生方法以及从合成气体制造烃的方法 |
CN101811050A (zh) * | 2010-05-05 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | 一种有机疏水改性钴基费托合成催化剂及制备和应用 |
Non-Patent Citations (1)
Title |
---|
Designing a Capsule Catalyst and Its Application for direct synthesis of middle isoparaffins;Jiangjiang He;《Langmuir》;20050201;第21卷(第5期);第1699页右栏8-10行,第1700页左栏"Experimental Section(实验部分)"第1-6行, * |
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RU2642451C1 (ru) | 2018-01-25 |
AU2018205112B2 (en) | 2019-10-24 |
KR20160147872A (ko) | 2016-12-23 |
EP3135372A4 (en) | 2018-01-24 |
JP2017521227A (ja) | 2017-08-03 |
CN103920496A (zh) | 2014-07-16 |
AU2018205112A1 (en) | 2018-08-02 |
WO2015161701A1 (zh) | 2015-10-29 |
AU2018205112C1 (en) | 2020-01-23 |
US20170036198A1 (en) | 2017-02-09 |
US10363550B2 (en) | 2019-07-30 |
CA2946638A1 (en) | 2015-10-29 |
AU2015251403A1 (en) | 2016-12-08 |
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