CN102378648B - Co变换催化剂、co变换反应装置及气化气体的精制方法 - Google Patents
Co变换催化剂、co变换反应装置及气化气体的精制方法 Download PDFInfo
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- CN102378648B CN102378648B CN200980158504.3A CN200980158504A CN102378648B CN 102378648 B CN102378648 B CN 102378648B CN 200980158504 A CN200980158504 A CN 200980158504A CN 102378648 B CN102378648 B CN 102378648B
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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- B01J23/8871—Rare earth metals or actinides
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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- C—CHEMISTRY; METALLURGY
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- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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Abstract
本发明提供一种对气体中的一氧化碳(CO)进行改性的CO变换催化剂,所述CO变换催化剂将钼(Mo)或钴(Co)中的任意一方或两方作为活性成分,同时将担载该活性成分的钛(Ti)、硅(Si)、锆(Zr)及铈(Ce)中的任意一种或这些的混合·复合物的氧化物作为载体,使用该CO变换催化剂将气化炉(11)中生成的气化气体(12)中的CO转化成CO2,本发明的CO变换催化剂可以应用于具备耐卤素性的CO变换反应装置(15)。
Description
技术领域
本发明涉及一种将气化气体中的CO转化成CO2的CO变换催化剂及使用其的CO变换反应装置以及气化气体的精制方法。
背景技术
煤的有效利用作为在近年来的能源问题上的强有力的手段之一受到关注。
另一方面,为了将煤转换为附加值高的能量介质,需要煤气化技术、气体精制技术等尖端技术。
已提案有使用该气化气体进行发电的煤气化复合发电系统(专利文献1)。
该煤气化复合发电(Integrated coal.Gasification Combined Cycle:IGCC)是指将煤在高温高压的气化炉内转换成可燃性气体并以其气化气体为燃料利用燃气涡轮和蒸汽涡轮进行复合发电的系统。
将这一个例子示于图2。图2为表示现有技术的煤气化发电设备的说明图。如图2所示,煤气化发电设备100进行的操作是,用气化炉102气化煤101,获得作为生成气体的气化气体103后,用洗涤器等脱尘装置104除尘后,使用COS转化装置105将COS转化成H2S后,用CO变换反应装置106使其发生CO变换反应后,用H2S/CO2回收装置107回收CO2,同时除去气体中的H2S。
用上述H2S/CO2回收装置107处理后的生成气体108被供给于作为发电机构的燃气涡轮110的燃烧器111,在此进行燃烧生成高温·高压的燃烧气体,利用该燃烧气体驱动涡轮112。涡轮112和发电机113相连接,通过涡轮112驱动而使发电机113产生电力。由于驱动涡轮112后的废气114还保持500~600℃的温度,因此,优选送入HRSG(Heat Recovery Steam Generator:废热回收锅炉)115中回收热能。在HRSG115中,利用废气的热能生成蒸汽,利用该蒸汽驱动蒸汽涡轮116。对于用HRSG115回收热能后的废气,用脱硝装置(未图示)除去废气中的NOx成分后,经由烟筒117排放到大气中。需要说明的是,图2中,符号120图示空气、121图示空气分离装置、122图示气化空气压缩机、123图示气化空气、124图示水蒸汽、125图示H2S/CO2处理系统。
这样,对于在气化炉102中气化了的气化气体103,在分离CO2前,需要将气化气体中所含的CO转化成CO2的所谓的CO变换反应装置106。
该CO变换反应以通过下述式(1)的反应获得作为有效成分的CO2和H2的方式来进行。
CO+H2O→CO2+H2...(1)
需要说明的是,作为促进该CO变换反应的催化剂提案有各种CO变换催化剂,可示例例如担载于氧化铝质载体上的钼(Mo)-钴(Co)类催化剂(专利文献1)。
另外,利用CO变换反应装置106,可将气化气体103中大量包含的CO转化成H2,因此,除作为涡轮用的气体的用途以外,也可用作例如甲醇、氨等合成品合成用的气体。
先行技术文献
专利文献
专利文献1:日本特开2004-331701号公报
专利文献2:日本特公昭59-2537号公报
发明内容
发明要解决的问题
但是,燃料的煤101中含有卤素(主要为Cl),在利用气化炉102中的部分氧化反应对煤进行气化时,可以确认形成例如氯化氢(HCl),攻击作为CO变换催化剂的载体的氧化铝,发生劣化。
因此,作为煤气化发电设备100,需要在CO变换反应装置106的上游侧充分除去氯化氢(HCl)。因此,需要设置利用气液接触的洗涤器等脱尘装置104,但为了用该脱尘装置104进行除去,必须将在气化炉102中气化了的气化气体103的温度从350℃暂时降至接近160℃,存在热效率不佳的问题。
因此,迫切期望开发一种即使存在氯化氢(HCl)劣化也少的高性能催化剂。
本发明的课题在于,鉴于上述问题,提供一种即使存在氯化氢(HCl)劣化也少的CO变换催化剂及使用该催化剂的CO变换反应装置、以及气化气体的精制装置。
用于解决问题的手段
用于解决上述课题的本发明的第一发明为CO变换催化剂,其特征在于,对气体中的一氧化碳(CO)进行改性,将钼(Mo)或钴(Co)中的任意一方或两方作为活性成分,同时将担载该活性成分的钛(Ti)、硅(Si)、锆(Zr)及铈(Ce)中的任意一种作为载体。
第二发明为第一发明中所述的CO变换催化剂,其特征在于,所述载体包含存在至少2种元素的复合氧化物。
第三发明为第一发明所述的CO变换催化剂,其特征在于,所述载体包含存在钛(Ti)、硅(Si)、锆(Zr)及铈(Ce)中的至少一种元素和铝(Al)元素的复合氧化物。
第四发明为第一发明至第三发明中任一项所述的CO变换催化剂,其特征在于,钼(Mo)的添加量为1~50重量%,钴(Co)的添加量为1~30重量%。
第五发明为一种CO变换反应装置,其特征在于,将第一发明至第四发明中任一项所述的CO变换催化剂填充在反应塔内。
第六发明为一种气化气体的精制方法,其用过滤器除去在气化炉中获得的包含卤化物的气化气体中的烟尘;然后,使用第一发明至第四发明中任一项所述的CO变换催化剂进行CO变换反应;其后,利用湿式洗气装置进一步净化CO变换反应后的气化气体;接着,除去气化气体中的二氧化碳。
发明效果
根据本发明,由于其为耐卤素性的催化剂,因此,可以在CO变换反应装置的下游侧设置湿式洗气装置,在不暂时降低气体温度的情况下进行CO变换反应,由此可以尝试提高能效。
另外,在用于现有反应设备时,由于对滑移卤化物(slip halide)具有耐性,因此可以尝试提高可靠性。
附图说明
图1是具备填充有CO变换催化剂的CO变换反应装置的气化气体精制系统的概略图。
图2是表示现有技术的煤气化发电设备的说明图。
具体实施方式
下面,参照附图详细地说明该发明。需要说明的是,本发明并不受该实施例限制。另外,在下述实施例中的构成要素中,包含所属领域的技术人员可以容易地设想的要素或实质上相同的要素。
实施例
参照附图对本发明的实施例中的CO变换催化剂及使用其的CO变换反应装置进行说明。图1为具备填充有CO变换催化剂的CO变换反应装置的气化气体精制系统的概略图。
如图1所示,气化气体精制系统10具备:对作为燃料F的煤进行气化的气化炉11、除去作为生成气体的气化气体12中的烟尘的过滤器13、备有将气化气体12中的CO转化成CO2的CO变换催化剂14的CO变换反应装置15、除去CO变换反应后的气化气体12中的卤素的湿式洗气装置16、降低气化气体12的温度的第1热交换器17、由吸收热交换后的气化气体12中的CO2的吸收塔18A和进行再生的再生塔18B构成的气体精制装置18。
图1中,符号20图示再生过热器、21图示加热气化气体12的第2热交换器、22图示水蒸气。
本发明的CO变换催化剂为对气体中的一氧化碳(CO)进行改性的CO变换催化剂,将钼(Mo)或钴(Co)中的任意一方或两方作为活性成分,同时将担载该活性成分的钛(Ti)、硅(Si)、锆(Zr)及铈(Ce)中的任意一种或这些的混合·复合物的氧化物作为载体。
载体使用钛(Ti)、硅(Si)、锆(Zr)及铈(Ce)中的任意一种,由此可以对气化气体中的卤化物具有耐性,可以使由气化炉11气化了的气化气体12立即进行CO变换反应。
这也可由如下结果来明确,即,如后述的试验例所示,测量作为CO变换反应的反应效率的指标的CO添加率(%)的结果,即使在氯化氢暴露后添加率的下降也低。
作为上述载体,优选为TiO2、SiO2、ZrO2、CeO2等氧化物。
另外,上述载体也可以包含存在这些元素中的至少2种元素的复合氧化物。需要说明的是,也包含复合氧化物和混合物并存的情况。
在此,作为获得的复合氧化物,可以示例例如:TiO2-ZrO2、TiO2-SiO2、TiO2-CeO2、CeO2-ZrO2、SiO2-ZrO2等复合氧化物。
进而,也可以示例使TiO2、SiO2、ZrO2、CeO2等氧化物中的任意一种和Al2O3组合而成的例如TiO2-Al2O3、ZrO2-Al2O3等复合氧化物。需要说明的是,构成复合氧化物的Al2O3单独使用时,如后述的试验例所示,卤素的劣化显著,因此不能用作载体,但是通过制成和TiO2等的复合氧化物可以缓和这种现象,可以用作载体。
在此,作为活性成分的上述钼(Mo)的添加量,可以设定为优选1~50重量%、特别优选6~18重量%。
作为钴(Co)的添加量,可以设定为优选1~30重量%、特别优选2~9重量%。
根据本发明,使用具有上述CO变换催化剂14的CO变换反应装置15,进行CO变换反应,然后,利用湿式洗气装置16进一步净化CO变换反应后的气化气体,接着,除去气化气体中的二氧化碳,可以获得精制气体19。
根据本实施例,如图1所示,来自气化炉11的气化气体12为350℃高温,但在维持其温度的状态下利用CO变换反应装置15使其发生CO变换反应,因此,气体温度没有下降,能量损失降低。
而且,本实施例中,在CO变换反应装置15中的反应结束后,在湿式洗气装置16中使气体温度下降,同时除去气体中的卤化物,然后用由吸收塔18A和再生塔18B构成的气体精制装置18进行气体精制。因而,不是象以往那样一下用洗气装置降低温度后再次升至高温而用CO变换反应装置106使其发生CO变换反应,可以构筑热均衡良好的系统构成。
在此,上述气体精制装置提案有对CO2或H2S利用化学吸附法进行精制及利用物理吸附进行精制等各种方法,没有特别限定。
另外,在气化气体12中混入了COS,可以在CO变换反应装置15的前后的任意一方设置COS转化催化剂装置,或者也可以在气体精制装置18中利用物理吸附手段来除去。
如上所述,根据本发明,在煤气化炉11中进行气化时,不会担心由煤F中的卤素引起的劣化,因此可以大幅度缓和变换反应装置15的配置的制约,由此,可以在气化炉11的下游侧的较高的气体温度下使其发生CO变换反应,其结果,可以实现热效率良好且高效的气体精制工艺。
[试验例]
以下,对表示本发明的效果的试验例进行说明。
[试验例1-1:浸渍(IMP)法]
将石原产业株式会社制造的氧化钛(TiO2(“MC-90”商品名))83.3g加入瓷制盘中,并以相对于最终获得的全部粉末量担载CoO 4wt%、担载MoO313wt%的方式添加溶解于100ml水中的六水合硝酸钴和四水合钼酸铵,然后,在瓷制盘上进行蒸发干燥浸渍。
然后,用干燥器将获得的粉末进行完全干燥后,在500℃下实施3小时(升温速度100℃/h)焙烧,由此获得粉末催化剂1-1。需要说明的是,本试验例的CoO/MoO3的担载量(wt%/wt%)为4/13。
将获得的粉末催化剂1-1用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂1-1(催化剂成分:Mo、Co;载体成分:TiO2)。
[试验例1-2:沉淀(PR)法]
将石原产业株式会社制造的氧化钛(TiO2(“MC-90”商品名))83.3g加入加有3L水的烧杯中,在其中以相对于最终获得的全部粉末量为CoO 4wt%的方式添加六水合硝酸钴。
对烧杯内进行搅拌使硝酸钴溶解后,在继续搅拌的状态下滴加使碳酸钠2.5mol%溶解于2L水中而成的溶液,使其沉淀。
接着,以相对于最终获得的全部粉末量担载MoO3 13wt%的方式添加四水合钼酸铵并搅拌溶解。
然后,在继续搅拌的状态下滴加1当量的硝酸水溶液,使其沉淀。
最后,用离心分离机进行洗涤过滤、干燥后,在500℃下实施3小时(升温速度100℃/h)焙烧,由此获得粉末催化剂1-2。需要说明的是,本试验例的CoO/MoO3的担载量(wt%/wt%)为4/13。
将获得的粉末催化剂1-2用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂1-2(催化剂成分:Mo、Co;载体成分:TiO2)。
[试验例1-3:共沉淀(CPR)法]
将林纯药株式会社制造的硫酸钛氧(TiOSO4(含有TiO2=32%))260.3g加入加有3L水的烧杯中,在其中以相对于最终获得的全部粉末量担载CoO4wt%的方式添加六水合硝酸钴。
对烧杯内进行搅拌使硝酸钴溶解后,在继续搅拌的状态下滴加使碳酸钠2.5mol%溶解于2L水中而成的溶液,使其沉淀。
接着,以相对于最终获得的全部粉末量担载MoO3 13wt%的方式添加四水合钼酸铵并搅拌溶解。
然后,在继续搅拌的状态下滴加1当量的硝酸水溶液,使其沉淀。
最后,用离心分离机进行洗涤过滤、干燥后,在500℃下实施3小时(升温速度100℃/h)焙烧,由此获得粉末催化剂1-3。需要说明的是,本试验例的CoO/MoO3的担载量(wt%/wt%)为4/13。
将获得的粉末催化剂1-3用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂1-3(催化剂成分:Mo、Co;载体成分:TiO2)。
[试验例1-4:溶胶-凝胶(SG)法]
将石原产业株式会社制造的氧化钛(TiO2(“MC-90”商品名))83.3g加入加有3L水的烧杯中,边搅拌边加入10ml的lmol·L的盐酸水溶液,然后以相对于最终获得的全部粉末量担载CoO 4wt%、担载MoO3 13wt%的方式添加六水合硝酸钴和氯化钼。
其后,在80℃×4小时的条件下搅拌加热后,加入150ml的0.5%的氨水溶液,获得凝胶化沉淀物。
最后,用离心分离机进行洗涤过滤、干燥后,在500℃下实施3小时(升温速度100℃/h)焙烧,由此获得粉末催化剂1-4。需要说明的是,本试验例的CoO/MoO3的担载量(wt%/wt%)为4/13。
将获得的粉末催化剂1-4用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂1-4(催化剂成分:Mo、Co;载体成分:TiO2)。
[试验例1-5:共聚凝胶(CSG)法(日文:共ゲル法)]
在加有3L水的烧杯中,边搅拌边添加10ml的lmol·L的盐酸水溶液,然后以相对于最终获得的全部粉末量担载CoO 4wt%、担载MoO3 13wt%的方式添加六水合硝酸钴和氯化钼。
其后,在80℃×5小时的条件下搅拌加热后,加入283.9g异丙氧基钛(Ti(Oi-C3H7)4)并进一步熟成1小时,从而获得凝胶化沉淀物。
最后,用离心分离机进行洗涤过滤、干燥后,在500℃下实施3小时(升温速度100℃/h)焙烧,由此获得粉末催化剂1-5。需要说明的是,本试验例的CoO/MoO3的担载量(wt%/wt%)为4/13。
将获得的粉末催化剂1-5用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂1-5(催化剂成分:Mo、Co;载体成分:TiO2)。
[试验例2:改变浸渍法的组成及原料]
将试验例1的TiO2更换成林纯药株式会社制造的氧化锆(ZrO2),将CoO/MoO3的担载量(wt%/wt%)更换成2/10,除此之外,和试验例1-1同样操作,获得粉末催化剂2。
最后,将获得的粉末催化剂2用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂2(催化剂成分:Mo、Co;载体成分:ZrO2)。
[试验例3:改变浸渍法的组成及原料]
下面,将试验例1的TiO2/MoO3原料更换成15%ZrO2-85%TiO2复合氧化物/硫代钼酸铵,将CoO/MoO3的担载量(wt%/wt%)更换成5/11,除此之外,和试验例1-1同样操作,获得粉末催化剂3。
最后,将获得的粉末催化剂3用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂3(催化剂成分:Mo、Co;载体成分:ZrO2/TiO2)。
[试验例4:改变浸渍法的组成及原料]
下面,将试验例1的TiO2/MoO3原料更换成80TiO2-20A12O3复合氧化物/氯化钴/硫代钼酸铵,将CoO/MoO3的担载量(wt%/wt%)更换成4/13,除此之外,和试验例1-1同样操作,获得粉末催化剂4。
最后,将获得的粉末催化剂4用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂4(催化剂成分:Mo、Co;载体成分:TiO2/Al2O3)。
[试验例5:改变沉淀法的组成及原料]
将试验例1-2的TiO2/MoO3原料更换成20CeO2-80TiO2复合氧化物/磷钼酸,将CoO/MoO3的担载量(wt%/wt%)更换成9/6,除此之外,和试验例1-2同样操作,获得粉末催化剂5。
将获得的粉末催化剂5用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂5(催化剂成分:Mo、Co;载体成分:CeO2/TiO2)。
[试验例6:改变沉淀法的组成及原料]
下面,将试验例1-2的TiO2/MoO3原料更换成80OCeO2-20ZrO2复合氧化物/氯化钴/硫代钼酸铵,将CoO/MoO3的担载量(wt%/wt%)更换成4/15,除此之外,和试验例1-2同样操作,获得粉末催化剂6。
最后,将获得的粉末催化剂6用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂6(催化剂成分:Mo、Co;载体成分:CeO2/ZrO2)。
[试验例7:改变沉淀法的组成及原料]
下面,将试验例1-2的TiO2/MoO3原料更换成15SiO2-85Al2O3复合氧化物/硫酸钴,将CoO/MoO3的担载量(wt%/wt%)更换成3/12,除此之外,和试验例1-2同样操作,获得粉末催化剂7。
将获得的粉末催化剂7用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂7(催化剂成分:Mo、Co;载体成分:SiO2/Al2O3)。
[试验例8:改变共沉淀法的组成及原料]
下面,将试验例1-2的TiO2/MoO3原料更换成95TiO2-5SiO2复合氧化物/硫酸钴,将CoO/MoO3的担载量(wt%/wt%)更换成5/7,除此之外,和试验例1-2同样操作,获得粉末催化剂8。
将获得的粉末催化剂8用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂8(催化剂成分:Mo、Co;载体成分:SiO2/TiO2)。
[试验例9:改变溶胶-凝胶法的组成及原料]
将试验例1-4的TiO2/MoO3原料更换成第一稀元素化学制造的CeO2/醋酸钴/钼酸钠,将CoO/MoO3的担载量(wt%/wt%)更换成7/8,除此之外,和试验例1-4同样操作,获得粉末催化剂9。
接着,将获得的粉末催化剂9用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂9(催化剂成分:Mo、Co;载体成分:CeO2)。
[试验例10:改变溶胶-凝胶法的组成及原料]
下面,将试验例1-4的TiO2/MoO3原料更换成10ZrO2-90Al2O3复合氧化物/醋酸钴/磷钼酸,将CoO/MoO3的担载量(wt%/wt%)更换成8/18,除此之外,和试验例1-4同样操作,获得粉末催化剂10。
接着,将获得的粉末催化剂10用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂10(催化剂成分:Mo、Co;载体成分:ZrO2/Al2O3)。
[试验例11:改变共聚凝胶法的组成及原料]
将试验例1-5的TiO2原料更换成硅酸乙酯Si(OC2H5)4,将CoO/MoO3的担载量(wt%/wt%)更换成6/14,除此之外,和试验例1-5同样操作,获得粉末催化剂11。
将获得的粉末催化剂11用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得催化剂11(催化剂成分:Mo、Co;载体成分:SiO2)。
[比较例1]
将试验例1-1的TiO2更换成林纯药株式会社制造的A12O3,除此之外,和试验例1-1同样操作,获得比较粉末催化剂1。
接着,将获得的比较粉末催化剂1用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得比较催化剂1(催化剂成分:Mo、Co;载体成分:A12O3)。
[比较例2]
使碳酸钠2.5mol%溶解于2L水中,保温在60℃,将该碱性溶液设定为溶液A。接着,使硝酸铝0.123mol及硝酸锌0.092mol溶解于400ml水中,保温在60℃,将该酸性溶液设定为溶液B。另外,使硝酸铜0.22mol溶解于400ml水中,保温在60℃,将由此而成的酸性溶液设定为溶液C。
首先,边搅拌边在溶液A中用30分钟均匀地滴加溶液B,获得沉淀生产液D。接着,将溶液C用30分钟均匀地滴加在上述沉淀生产液D中,获得含有铝、锌及铜的沉淀生产液F。
通过将沉淀生产液F直接搅拌2小时来进行熟化,接着进行充分洗涤以使其检测不到沉淀生产液F的滤液及Na离子、NO离子。进而,在100℃下干燥24小时,然后在300℃下焙烧3小时,由此获得比较粉末催化剂。将该比较粉末催化剂设定为比较粉末催化剂2。
接着,将获得的比较粉末催化剂2用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得比较催化剂2(催化剂成分:Cu、Zn;载体成分:Al2O3)。
[比较例3]
将比较例2的硝酸铝设定为0.098mol、将替代硝酸锌的硝酸铁设定为0.144mol、将替代硝酸铜的硝酸铬设定为0.079mol,除此之外,和比较例2同样操作,获得比较粉末催化剂3。
接着,将获得的比较粉末催化剂3用30ton的加压成型机使粉末固定化后,进行破碎以使其粒径为2~4mm的范围,然后,进行筛分获得比较催化剂3(催化剂成分:Cr、Fe;载体成分:Al2O3)。
对于试验,利用如下装置来评价催化剂活性,所述装置为:在内径20mm的管型反应管中填充15.8cc的催化剂,用质量流量控制器可以控制气体组成、流量,还可以用电炉控制催化剂层温度。
在此,作为评价条件,设定为:H2/CO/CO2=30/50/20mol%、S/CO=2.0、压力0.1PMa、温度350℃。气体量设定为1,500h-1(23.7L/h)。
另外,对于催化剂活性的比较而言,设定为以催化剂层入口、出口的气体流量变化定义为下述所示的CO转化率的参数。
CO转化率(%)=(1-(催化剂层出口CO气体流量(mol/h)/催化剂层入口CO气体流量(mol/h))
另外,对于氯化氢的暴露试验而言,求出在HCl浓度100ppm下150小时后的CO转化率。
将该结果示于表1。
如表1所示,对于本试验例的催化剂,即使在HCl暴露后,所有催化剂的CO转化率都良好,但是,比较例的催化剂的CO转化率大幅度降低或失去活性。另外,对于比表面积,本试验例的催化剂在暴露后也没有看到大幅度降低,但是比较例的催化剂可以确认降低为一半以下。
由此可以断定,本发明的催化剂可有效用作耐卤性的CO变换催化剂。
[试验例12]
相对于试验例1-1中获得的粉末催化剂1-1100份添加高岭土50份、醋酸纤维素10份及离子交换水,在大气中进行5分钟混炼、在真空中进行5分钟混炼后,使用4.2mmp(在此,p为加上气体流通的网眼和内壁值的值)、内壁厚0.6mm的格子状口模挤出,然后进行干燥并在500℃下焙烧2小时,由此获得蜂窝状的催化剂12。
[试验例13]
将试验例12的粉末催化剂1-1更换成粉末催化剂8,除此之外,和试验例12同样操作,获得蜂窝状的催化剂13。
[比较例4]
将试验例12的粉末催化剂1-1更换成比较粉末催化剂1,除此之外,和试验例12同样操作,获得蜂窝状的比较催化剂4。
将该结果示于表2。需要说明的是,和上述试验同样操作来进行试验。
[表2]
由该结果可确认,对于试验例1及8的催化剂,使用蜂窝状的催化剂进行试验的结果,和加压成型品的性能大致相同。由此,与使用加压成型品的催化剂相比,可期待降低压损。
产业上的可利用性
如上所述,使用本发明的CO变换催化剂,在煤气化炉中进行气化时,不担心由煤中的卤素引起的劣化,因此可以大幅度缓和变换反应装置的配置的制约。从而可以提供一种热效率良好且高效的气体精制工艺。
符号说明
10气化气体精制系统
11气化炉
12气化气体
13过滤器
14CO变换催化剂
15CO变换反应装置
16湿式洗气装置
17第1热交换器
18气体精制装置
Claims (3)
1.一种CO变换催化剂,其特征在于,
所述CO变换催化剂是对气体中的一氧化碳(CO)进行改性的耐卤素性的CO变换催化剂,且将钼(Mo)和钴(Co)作为活性成分,且担载所述活性成分的载体是选自下述(a)~(f)中的任意一种,
(a)锆(Zr)和钛(Ti)的复合氧化物、
(b)铈(Ce)和钛(Ti)的复合氧化物、
(c)铈(Ce)和锆(Zr)的复合氧化物、
(d)硅(Si)和铝(Al)的复合氧化物、
(e)硅(Si)和钛(Ti)的复合氧化物、
(f)锆(Zr)和铝(Al)的复合氧化物,
并且所述钼(Mo)的添加量为6~18重量%,所述钴(Co)的添加量为2~9重量%。
2.一种CO变换反应装置,其特征在于,
将权利要求1所述的CO变换催化剂填充在反应塔内而成。
3.一种气化气体的精制方法,其中,
用过滤器除去在气化炉中获得的包含卤化物的气化气体中的烟尘,
然后,使用下述的CO变换催化剂,进行CO变换反应,
之后,利用湿式洗气装置进一步净化CO变换反应后的气化气体,
接着,除去气化气体中的二氧化碳,
所述CO变换催化剂是对气体中的一氧化碳(CO)进行改性的CO变换催化剂,且将钼(Mo)或钴(Co)中的任意一方或两方作为活性成分,且将担载所述活性成分的钛(Ti)、硅(Si)、锆(Zr)及铈(Ce)中的任意一种作为载体。
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US20150299592A1 (en) * | 2012-12-28 | 2015-10-22 | Mitsubishi Heavy Industries, Ltd. | Co shift catalyst, co shift reactor, and method for purifying gasification gas |
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