CN114080273A - 烃重整催化剂和烃重整装置 - Google Patents
烃重整催化剂和烃重整装置 Download PDFInfo
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 145
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 145
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 144
- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 238000002407 reforming Methods 0.000 title claims abstract description 124
- 239000007789 gas Substances 0.000 claims abstract description 56
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 13
- 229910002761 BaCeO3 Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 13
- 229910052788 barium Inorganic materials 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 9
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- 239000012071 phase Substances 0.000 description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 24
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 23
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 230000000977 initiatory effect Effects 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 9
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- 239000000463 material Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000012790 confirmation Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000629 steam reforming Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
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- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
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- 230000003247 decreasing effect Effects 0.000 description 2
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- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 229910052746 lanthanum Inorganic materials 0.000 description 1
- -1 lanthanum aluminate Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Abstract
烃重整催化剂,是由烃类气体生成含氢和一氧化碳的合成气体时所使用的烃重整催化剂,包含具有钙钛矿结构的复合氧化物,复合氧化物具有以BaCeO3为主成分的结晶相,且含有Ru。
Description
技术领域
本发明涉及烃重整催化剂和具备这样的烃重整催化剂的烃重整装置,所述烃重整催化剂在由烃类气体生成含氢和一氧化碳的合成气体时使用。
背景技术
已知有使用催化剂,由烃类气体得到含氢和一氧化碳的合成气体的方法。作为用于烃类气体的重整反应的催化剂,已知有在氧化铝等的基体上担载镍的镍系催化剂、担载钌的钌系催化剂(参照专利文献1),在氧化铝等的基体上担载铑的铑系催化剂(参照专利文献2)等。
另外,已知有以抑制碳析出和提高低温下的活性为目的,在使用了作为钙钛矿型化合物的铝酸镧、钛酸锶、钛酸钡的担体上担载铑、钴和镍作为活性成分的催化剂(参照专利文献3)。
作为一般的金属担载催化剂的制造方法,使用将作为担体的氧化物浸于金属盐等的溶液中后,通过进行热处理而使活性金属分散在担体表面的浸渍法(专利文献1~3)。
还有,因为担体成分要求有高的热稳定性和强度,所以通过在高温下进行热处理而被充分烧结,相对于此,担载金属为了得到高活性而需要维持分散性。因此,为了将热处理工序中的凝集抑制在最低限度,如上述的浸渍法那样,使用不同于担体合成的制造工序,在比较低温的热处理条件下固定在担体上。
但是,由浸渍法制造的催化剂,虽然能够维持高的金属分散性,但需要与担体成分的合成工序不同,担载金属成分的浸渍工序。另外,因为金属成分经过比较低温的热处理而被附着,所以金属与担体之间的结合弱,碳析出导致的活性降低成为问题。
因此,作为不使用浸渍工序的催化剂的制造方法,提出有通过固相合成来合成含有BaNiY2O5的复合氧化物,由此使Ni成分的分散性提高的方法(专利文献4)。
现有技术文献
专利文献
专利文献1:日本特开平8-231204号公报
专利文献2:日本特开平9-168740号公报
专利文献3:日本特开2006-346598号公报
专利文献4:日本特开2015-136668号公报
然而,专利文献4所述的催化剂,虽然能够抑制碳析出,但说不上活性充分高,尚有改善的余地。
发明内容
本发明正是要解决上述课题,其目的在于,提供一种活性高的烃重整催化剂、和具备这样的烃重整催化剂的烃重整装置。
本发明的烃重整催化剂,其特征在于,是在由烃类气体生成含氢和一氧化碳的合成气体时所使用的催化剂,其中,包含具有钙钛矿结构的复合氧化物,所述复合氧化物具有以BaCeO3为主成分的结晶相,并且含有Ru。
根据本发明,能够提供活性高的烃重整催化剂、和具备这样的烃重整催化剂的烃重整装置。
附图说明
图1是表示烃重整装置的概略结构的图。
图2是表示实施例2和实施例26的烃重整催化剂的X射线衍射花样的图。
具体实施方式
以下展示本发明的实施方式,具体地说明本发明的特征。
本发明的烃重整催化剂,是在由烃类气体生成含氢和一氧化碳的合成气体时所使用的催化剂,包含具有钙钛矿结构的复合氧化物,复合氧化物满足如下要件:具有以BaCeO3为主成分的结晶相,并且含有Ru(以下,称为本发明的要件)。
作为被处理气体的烃类气体,例如,能够使用以丙烷为主成分的丙烷气和以甲烷为主成分的天然气。另外,也能够使用使汽油或煤油、甲醇或乙醇等的液态烃气化而得到的烃类气体。
列举丙烷气的水蒸气重整为例,说明由烃类气体合成含氢和一氧化碳的合成气体的反应。丙烷气的水蒸气重整由下式(1)表示。
C3H8+3H2O→7H2+3CO (1)
但是,由烃类气体生成含氢和一氧化碳的合成气体的方法不限定于水蒸气重整。例如,除水蒸气以外,也包含氧和二氧化碳或它们的混合物。含二氧化碳时的重整反应,由下式(2)表示。
C3H8+3CO2→4H2+6CO (2)
图1是表示由至少含烃的被处理气体生成含氢和一氧化碳的合成气体的烃重整装置100的概略结构的图。烃重整装置100具备:被处理气体流通的管1;加热在管1中流通的被处理气体的加热部2;配置在管1内部的、与被处理气体接触的位置的烃重整催化剂3。烃重整催化剂3是满足本发明的要件的催化剂,包含具有钙钛矿结构的复合氧化物,复合氧化物具有以BaCeO3为主成分,并含有Ru的结晶相。还有,被处理气体自身为充分高温时,能够省略加热部2。
在管1的上游侧连接有供气管4。烃从烃供给源6被供给到供气管4。但是,烃供给源6也可以设于供气管4的前段。另外,在从烃供给源6被供给的烃中也可以包含其他的成分。
在管1的下游侧连接有排气管5,所述排气管5用于排出经重整而得到的含氢和一氧化碳的合成气体。在排气管5上设有氢引出口7,构成为能够引出合成气体中包含的氢。例如,可以形成为在排气管5内设置CO变换器,除去合成气体中所含的一氧化碳,从氢引出口7引出氢。
(实施例1~24)
作为烃重整催化剂的材料,准备BaCO3、ZrO2、CeO2、Y2O3和RuO2,使Ba:Zr:Ce:Y:Ru的摩尔比为表1所示的比例而进行称量,加入砾石、水和粘合剂进行湿法混合,得到混合物。将所得到的混合物在烘箱内以120℃的温度进行干燥后,进行粉碎、分级,由此成为0.5mm以上且0.7mm以下大小的粒状。其后,通过对于粒状试料在空气中以1000℃、1小时的条件进行烧成,从而得到实施例1~24的烃重整催化剂。
实施例1~24的烃重整催化剂是满足本发明的要件的催化剂。如表1所示,实施例1~24的烃重整催化剂含Ba、Zr、Ce、Y和Ru。Ce对于Ba的摩尔比为0.10以上且0.70以下,Ru对于Ba的摩尔比为0.04以上且0.43以下,Y对于Ba的摩尔比为0.05以上且0.50以下,Zr对于Ba的摩尔比为0.10以上且0.80以下。另外,Zr和Ce和Y的合计量对于Ba的摩尔比为0.71以上且1.67以下。
(实施例25~28)
作为烃重整催化剂的材料,准备BaCO3、ZrO2、CeO2和RuO2,使Ba:Zr:Ce:Ru的摩尔比为表1所示的比例而进行称量,加入砾石、水和粘合剂进行湿式混合,得到混合物。之后,通过与制作实施例1~24的烃重整催化剂的方法相同的方法,制作实施例25~28的烃重整催化剂。
实施例25~28的烃重整催化剂是满足本发明的要件的催化剂。如表1所示,实施例25~28的烃重整催化剂含Ba、Zr、Ce和Ru。
(实施例29~32)
作为烃重整催化剂的材料,准备BaCO3、CeO2、Y2O3和RuO2,使Ba:Ce:Y:Ru的摩尔比为表1所示的比例进行称量,加入砾石、水和粘合剂进行湿法混合,得到混合物。之后,通过与制作实施例1~24的烃重整催化剂的方法相同的方法,制作实施例29~32的烃重整催化剂。
实施例29~32的烃重整催化剂是满足本发明的要件的催化剂。如表1所示,实施例29~32的烃重整催化剂含Ba、Ce、Y和Ru。
(实施例33)
作为烃重整催化剂的材料,准备BaCO3、CeO2和RuO2,使Ba:Ce:Ru的摩尔比为表1所示的比例进行称量,加入砾石、水和粘合剂进行湿法混合,得到混合物。之后,通过与制作实施例1~24的烃重整催化剂的方法相同的方法,制作实施例33的烃重整催化剂。
实施例33的烃重整催化剂是满足本发明的要件的催化剂。如表1所示,实施例33的烃重整催化剂含Ba、Ce和Ru。
还有,上述的实施例1~33的烃重整催化剂,在其制作工序中,不需要用于使担体担载金属成分的浸渍工序。
(比较例1)
作为烃重整催化剂的材料,准备BaCO3、ZrO2、CeO2和RuO2,使Ba:Zr:Ce:Ru的摩尔比为表1所示的比例进行称量,加入砾石、水和粘合剂进行湿法混合,得到混合物。该混合物的Ba:Zr:Ce:Ru的摩尔比,与制作实施例26的烃重整催化剂时所用的材料的Ba:Zr:Ce:Ru的摩尔比相同。之后,除了使烧成温度为500℃以外,通过均与制作实施例26的烃重整催化剂的方法相同的方法,制作比较例1的烃重整催化剂。比较例1的烃重整催化剂是不满足本发明的要件的催化剂。
(比较例2)
作为烃重整催化剂的材料,准备BaCO3、ZrO2、CeO2、Y2O3和RuO2,使Ba:Zr:Ce:Y:Ru的摩尔比为表1所示的比例进行称量,加入砾石、水和粘合剂进行湿法混合,得到混合物。该混合物的Ba:Zr:Ce:Y:Ru的摩尔比,与制作实施例2的烃重整催化剂时所用的材料的Ba:Zr:Ce:Y:Ru的摩尔比相同。之后,除了使烧成温度为500℃以外,通过均与制作实施例2的烃重整催化剂的方法相同的方法,制作比较例2的烃重整催化剂。比较例2的烃重整催化剂是不满足本发明的要件的催化剂。
<结晶相的确认>
以研钵粉碎上述的实施例1~33和比较例1~2的烃重整催化剂,通过粉末XRD测量,确认结晶相。在粉末XRD测量中,作为X射线使用Cu-Kα1。
表1中显示在实施例1~33和比较例1~2的烃重整催化剂中确认到的结晶相和组成(摩尔比)。
[表1]
在实施例1~33的烃重整催化剂中,确认到具有钙钛矿结构的复合氧化物的结晶相,具体来说,就是确认到存在以BaCeO3为主成分的结晶相。另外,在实施例1~28的烃重整催化剂中,确认到存在以BaCeO3为主成分的结晶相、和以BaZrO3为主成分的结晶相。
还有,在一些实施例的烃重整催化剂中,根据组成比,也确认到BaCO3和Y2O3等异相。但是,即使在这些烃重整催化剂中,作为具有钙钛矿结构的复合氧化物的主要的结晶相,在不包含以BaZrO3为主成分的结晶相时,是以BaCeO3为主成分的结晶相,在包含以BaZrO3为主成分的结晶相时,是以BaCeO3为主成分的结晶相和以BaZrO3为主成分的结晶相。
在图2中显示实施例2和实施例26的烃重整催化剂的X射线衍射花样。如图2所示,在实施例2和实施例26的烃重整催化剂中,能够确认到存在以BaZrO3为主成分的结晶相、和以BaCeO3为主成分的结晶相。另一方面,未确认到由RuO2和Ru单体引起的衍射线。另外,在催化剂制作时的原料中包含Y2O3的实施例2的烃重整催化剂中,未确认到由Y2O3引起的衍射线。
即,Y和Ru分别存在于以BaZrO3为主成分的结晶相、和以BaCeO3为主成分的结晶相之中的至少一方的结构中。换言之,Y和Ru分别作为构成具有钙钛矿结构的复合氧化物的一个成分存在。
同样,在实施例1、3~24和29~32的烃重整催化剂中,Y和Ru也分别作为构成具有钙钛矿结构的复合氧化物的一个成分存在。另外,在复合氧化物中不包含Y的实施例25~28和33的烃重整催化剂中,Ru作为构成具有钙钛矿结构的复合氧化物的一个成分存在。
预先对于构成各实施例的烃重整催化剂的复合氧化物的钙钛矿结构进行说明。实施例1~24的烃重整催化剂中,钙钛矿结构至少由Ba、Zr、Ce、Y和Ru构成。在实施例25~28的烃重整催化剂中,钙钛矿结构至少由Ba、Zr、Ce和Ru构成。在实施例29~32的烃重整催化剂中,钙钛矿结构至少由Ba、Ce、Y和Ru构成。在实施例33的炭化氢重整催化剂中,钙钛矿结构至少由Ba、Ce和Ru构成。
另一方面,比较例1的烃重整催化剂,因为制作时的烧成温度为500℃,低于具有钙钛矿结构的复合氧化物的生成温度,所以确认到的是配料中使用的BaCO3、ZrO2、CeO2和RuO2的混合物。同样,比较例2的烃重整催化剂中,也确认到的是配料中使用的BaCO3、ZrO2、CeO2、Y2O3和RuO2的混合物。
<组成的确认>
用研钵细细粉碎实施例1~33的烃重整催化剂和比较例1~2的烃重整催化剂,对于所得到的粉末由X射线荧光分析(XRF分析)进行组成分析。其结果确认到,在进行了组成分析的全部烃重整催化剂中,维持着称量时分配的元素摩尔比,没有因加热烧成处理造成Ru成分减少等的元素摩尔比的变化。
在此,一般的Ru系催化剂若在含氧气氛中被高温加热,则Ru成分成为RuO4升华,Ru的含量减少。但是,满足本发明的要件的实施例1~33的烃重整催化剂,因为Ru存在于以BaZrO3为主成分的结晶相、和以BaCeO3为主成分的结晶相之中的至少一方的结构中,所以认为不会发生像上述这样的Ru减少。
<重整评价>
分别粉碎实施例1~33和比较例1~2的烃重整催化剂,进行分级,而形成0.5mm~0.7mm的大小后,通过以下的方法,进行作为烃类气体的丙烷气的水蒸气重整评价试验。
在图1所示的烃重整装置100的管1内,填充由上述方法制作的烃重整催化剂0.3g,通过加热部2以600℃进行了加热。而后,从供气管4导入如下原料气体:以360cc/分的流量导入氮(N2),以7cc/分的流量导入丙烷(C3H8),以60cc/分的流量导入水蒸气(H2O),以60cc/分的流量导入二氧化碳(CO2)。
导入管1内的原料气体被重整,含氧和一氧化碳的合成气体被从排气管5排出。被从排气管5排出的合成气体,经冷却式疏水器除去水分后,导入到气体分析装置(气相色谱仪),测量氢浓度。
在此,计算上述的气体分压和温度条件下的平衡气体组成时,平衡状态下的氢气浓度的比例,若除去水分则为8.1体积%。因此,导入的原料气体的反应100%进行时,从排气管5排出的氢在平衡状态下的浓度(以下,称为平衡氢浓度)为8.1体积%。
(I)初始活性的确认
原料气体从导入起最初的1小时作为不存在硫成分的状态,测量1小时后的氢浓度,确认烃重整催化剂的初始活性。表2中,显示使用各实施例和比较例的烃重整催化剂时,从排气管5排出的氢的浓度(初始的氢浓度)与初始活性的平衡到达率。初始活性的平衡到达率由下式(3)定义。
初始活性的平衡到达率=初始的氢浓度/平衡氢浓度×100(3)
(II)硫劣化后的特性确认
上述初始活性的确认后,以相对于原料气体的合计流量487cc/分成为50ppm的比例来混合SO2气体,测量1小时后的氢气浓度,确认硫存在下的催化剂的活性劣化。表2中显示使用各实施例和比较例的烃重整催化剂时,在硫存在下,1小时后从排气管5排出的氢的浓度与平衡到达率。在表2中表述为“硫劣化后”的氢浓度,和“硫劣化后的平衡到达率”。硫劣化后的平衡到达率,由下式(4)定义。
硫劣化后的平衡到达率=硫劣化后的氢浓度/平衡氢浓度×100(4)
(III)加热处理后的特性确认
上述硫劣化后的特性确认后,一边向管1中以360cc/分的流量导入氮(N2),以60cc/分的流量导入水蒸气(H2O),以60cc/分的流量导入二氧化碳(CO2),一边将烃重整催化剂加热至700℃,在该状态进行1小时加热处理。其后,将温度降至600℃,再以360cc/分的流量导入氮(N2),以7cc/分的流量导入丙烷(C3H8),以60cc/分的流量导入水蒸气(H2O),以60cc/分的流量导入二氧化碳(CO2),测量1小时后的氢浓度,确认加热处理后的烃重整催化剂的活性。
表2中,显示使用各实施例和比较例的烃重整催化剂时,在加热处理后从排气管5排出的氢的浓度和由加热带来的恢复率。加热带来的恢复率由下式(5)定义。
加热带来的恢复率=(加热处理后的氢浓度-硫劣化后的氢浓度)/平衡氢浓度×100(5)
由式(5)求得的恢复率为正值时,表示通过加热处理,发生了硫劣化的烃重整催化剂恢复。
试验结束后,为了确认有无碳析出,将烃重整催化剂在N2气氛中冷却取出,通过TG-DTA(热重差热分析),确认因碳燃烧造成的催化剂的重量变化,但在进行了评价的全部实施例和比较例的烃重整催化剂中,未确认到碳析出。
[表2]
<初始活性>
如表2所示,使用满足本发明的要件的实施例1~33的烃重整催化剂时,初始活性的平衡到达率为67%以上。相对于此,使用不满足本发明的要件的比较例1~2的烃重整催化剂时,初始活性的平衡到达率处于37%以下的低值。
之所以满足本发明的要件的烃重整催化剂的初始活性高,考虑是由于在至少具有以BaCeO3为主成分的结晶相,并具有钙钛矿结构的复合氧化物中固溶分散有Ru成分,由此稳定化,能够抑制高温氧化条件下的Ru成分的凝集和挥发,其结果是活性提高。
另一方面,不满足本发明的要件的比较例的烃重整催化剂,因为不具有钙钛矿结构的结晶相,所以得不到上述这样的结构,即,Ru成分固溶分散于具有钙钛矿结构的复合氧化物中的结构,认为初始活性变低。
另外,满足本发明的要件的烃重整催化剂之中,使用Ru对于Ba的摩尔比为0.08以上有0.43以下的实施例2~33的烃重整催化剂时,初始活性的平衡到达率为96%以上,达到更高的值。因此,满足本发明的要件的烃重整催化剂,优选Ru对于Ba的摩尔比为0.08以上且0.43以下。
<抗硫性>
如表2所示,使用不满足本发明的要件的比较例1~2的烃重整催化剂时,硫劣化后的平衡到达率为0%。相对于此,使用满足本发明的要件的实施例1~33的烃重整催化剂时,硫劣化后的平衡到达率为19%以上。满足本发明的要件的烃重整催化剂,因为Ru成分固溶分散在复合氧化物中,所以结合力强,能够得到抑制硫等中毒成分的吸附和化合物生成的效果,认为具有高抗硫性。
另外,使用复合氧化物具有以BaCeO3为主成分的结晶相、和以BaZrO3为主成分的结晶相的实施例1~28的烃重整催化剂时,硫劣化后的平衡到达率为44%以上,达到更高的值。因此,满足本发明的要件的烃重整催化剂,优选复合氧化物还具有以BaZrO3为主成分的结晶相。具有钙钛矿结构的复合氧化物通过进一步具有以BaZrO3为主成分的结晶相,即使重整对象的原料气体中包含硫杂质时,也可以长时间发挥催化剂功能。
<加热带来的硫劣化的恢复>
如表2所示,满足本发明的要件的烃重整催化剂之中,使用复合氧化物中包含Y的实施例1~24和29~32的烃重整催化剂时,加热带来的恢复率为高于0%的值。即,这些烃重整催化剂,通过加热处理,发生了硫劣化的催化剂功能得到恢复。
因此,从通过加热处理使发生了硫劣化的催化剂功能恢复的观点出发,满足本发明的要件的烃重整催化剂,优选在复合氧化物中包含Y。
另外,在满足本发明的要件,复合氧化物的钙钛矿结构至少由Ba、Zr、Ce和Ru构成,不含Y的实施例25~28的烃重整催化剂之中,Ce对于Ba的摩尔比为0.50以上且0.70以下的实施例27~28的烃重整催化剂,加热带来的恢复率为高于0%的值。因此,复合氧化物的钙钛矿结构至少由Ba、Zr、Ce和Ru构成,不含Y的烃重整催化剂,优选Ce对于Ba的摩尔比为0.50以上且0.70以下。
通过使用通过加热而从硫劣化中恢复的烃重整催化剂,即使在含硫成分的反应环境下,也能够通过加热处理使劣化的催化剂功能恢复,从而持续地由烃类气体生成含氢和一氧化碳的合成气体。
本发明不受上述实施方式限定,在本发明的范围内,可以施加各种应用、变形。
例如,上述的实施例的烃重整催化剂是粒状的形态,但与一般的金属担载催化剂同样,也可以使处于粉末状的烃重整催化剂担载于陶瓷或金属制的基材上来使用。另外,也可以不使用基材,而是通过冲压成形或挤压成形等方法成形催化剂粉末,以颗粒状、环状或蜂窝状等的形态进行使用。
在上述实施方式中,列举作为烃类气体使用丙烷气的例子进行了说明,但烃类气体不限定于丙烷气。
符号说明
1 管
2 加热部
3 烃重整催化剂
4 供气管
5 排气管
6 烃供给源
7 氢引出口
100 烃重整装置
Claims (12)
1.一种烃重整催化剂,其特征在于,是由烃类气体生成含氢和一氧化碳的合成气体时所使用的催化剂,其中,
包含具有钙钛矿结构的复合氧化物,
所述复合氧化物,具有以BaCeO3为主成分的结晶相,且含有Ru。
2.根据权利要求1所述的烃重整催化剂,其特征在于,所述复合氧化物还具有以BaZrO3为主成分的结晶相。
3.根据权利要求2所述的烃重整催化剂,其特征在于,所述钙钛矿结构,至少包含Ba、Zr、Ce和Ru。
4.根据权利要求1~3中任一项所述的烃重整催化剂,其特征在于,所述复合氧化物中不含Y,Ce对于Ba的摩尔比为0.50以上且0.70以下。
5.根据权利要求2所述的烃重整催化剂,其特征在于,所述复合氧化物中包含Y。
6.根据权利要求5所述的烃重整催化剂,其特征在于,所述钙钛矿结构至少包含Ba、Zr、Ce、Y和Ru。
7.根据权利要求6所述的烃重整催化剂,其特征在于,所述Ce对于所述Ba的摩尔比为0.10以上且0.70以下。
8.根据权利要求6或7所述的烃重整催化剂,其特征在于,所述Ru对于所述Ba的摩尔比为0.04以上且0.43以下。
9.根据权利要求8所述的烃重整催化剂,其特征在于,所述Ru对于所述Ba的摩尔比为0.08以上且0.43以下。
10.根据权利要求6~9中任一项所述的烃重整催化剂,其特征在于,所述Y对于所述Ba的摩尔比为0.05以上且0.50以下。
11.根据权利要求6~10中任一项所述的烃重整催化剂,其特征在于,所述Zr和所述Ce和所述Y的合计量对于所述Ba的摩尔比为0.71以上且1.67以下。
12.一种烃重整装置,其特征在于,具备:至少含烃的被处理气体流通的管;配置在所述管的内部的、与所述被处理气体接触的位置的权利要求1~11中任一项所述的烃重整催化剂。
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