CN108472628B - 脱硝催化剂及其制造方法 - Google Patents
脱硝催化剂及其制造方法 Download PDFInfo
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- CN108472628B CN108472628B CN201780003339.9A CN201780003339A CN108472628B CN 108472628 B CN108472628 B CN 108472628B CN 201780003339 A CN201780003339 A CN 201780003339A CN 108472628 B CN108472628 B CN 108472628B
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- Prior art keywords
- catalyst
- vanadium pentoxide
- denitration catalyst
- denitration
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 187
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 199
- 239000013522 chelant Substances 0.000 claims description 20
- 238000011068 loading method Methods 0.000 claims description 15
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims 1
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000758 substrate Substances 0.000 abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 97
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 72
- 230000000052 comparative effect Effects 0.000 description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 42
- 235000006408 oxalic acid Nutrition 0.000 description 24
- 238000003795 desorption Methods 0.000 description 22
- 229910052720 vanadium Inorganic materials 0.000 description 20
- 230000000694 effects Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 17
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 14
- 229910001935 vanadium oxide Inorganic materials 0.000 description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
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- 238000003980 solgel method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000000691 measurement method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
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- 239000007789 gas Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical group NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
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- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229910002483 Cu Ka Inorganic materials 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021541 Vanadium(III) oxide Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YMNMFUIJDSASQW-UHFFFAOYSA-N distrontium;oxygen(2-);vanadium Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[V].[V].[Sr+2].[Sr+2] YMNMFUIJDSASQW-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- OGRLITDAVSILTM-UHFFFAOYSA-N lead(2+);oxido(dioxo)vanadium Chemical compound [Pb+2].[O-][V](=O)=O.[O-][V](=O)=O OGRLITDAVSILTM-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- KFAFTZQGYMGWLU-UHFFFAOYSA-N oxo(oxovanadiooxy)vanadium Chemical compound O=[V]O[V]=O KFAFTZQGYMGWLU-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- DUSYNUCUMASASA-UHFFFAOYSA-N oxygen(2-);vanadium(4+) Chemical compound [O-2].[O-2].[V+4] DUSYNUCUMASASA-UHFFFAOYSA-N 0.000 description 1
- 235000010603 pastilles Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明提供在以氨为还原剂的选择性催化还原反应时,在较低温度下的脱硝效率良好、并且不伴随SO2的氧化的催化剂。该脱硝催化剂是在基底上涂覆催化剂成分而成的脱硝催化剂,其中,所述催化剂成分中存在43wt%以上的五氧化二钒,所述催化剂成分的BET比表面积为30m2/g以上,所述脱硝催化剂用于在200℃以下的脱硝。
Description
技术领域
本发明涉及脱硝催化剂及其制造方法。更具体而言,本发明涉及在对通过使燃料燃烧而产生的排气进行净化时所使用的脱硝催化剂及其制造方法。
背景技术
作为通过燃料的燃烧而向大气中排出的污染物质之一,可举出氮氧化物(NO、NO2、NO3、N2O、N2O3、N2O4、N2O5)。氮氧化物会引起酸雨、臭氧层破坏、光化学烟雾等,对环境及人体造成严重影响,因此其处理已成为重要课题。
作为除去上述氮氧化物的技术,已知有以氨(NH3)为还原剂的选择性催化还原反应(NH3-SCR)。如专利文献1中记载的那样,作为用于选择性催化还原反应的催化剂,以氧化钛为载体、并负载有氧化钒的催化剂已被广泛使用。氧化钛由于对硫氧化物的活性低、并且稳定性高,因此被认为是最好的载体。
现有技术文献
专利文献
专利文献1:日本特开2004-275852号公报
发明内容
发明所要解决的课题
另一方面,氧化钒在NH3-SCR中起主要作用,但由于会将SO2氧化成SO3,因此不能负载1wt%左右以上的氧化钒。因此,通常以相对于载体为1wt%以下的量进行使用。与此同时,在现有的NH3-SCR中,在氧化钛载体上负载氧化钒(以及根据情况而负载氧化钨)而成的催化剂在低温时基本不会发生反应,因此不得不于350-400℃这样的高温进行使用。
然而,为了提高实施NH3-SCR的装置、设备的设计自由度、提高效率,要求开发出即使于低温也显示高氮氧化物还原率活性的催化剂。
本发明是鉴于上述课题而完成的,目的在于提供在以氨为还原剂的选择性催化还原反应时,低温时的脱硝效率良好、并且不伴随SO2的氧化的催化剂。
用于解决课题的手段
本发明涉及脱硝催化剂,其是在基底上涂覆催化剂成分而成的脱硝催化剂,其中,上述催化剂成分中存在43wt%以上的五氧化二钒(日文为“五酸化バナジウム”),上述催化剂成分的BET比表面积为30m2/g以上,上述脱硝催化剂用于在200℃以下的脱硝。
另外,优选上述催化剂成分的利用NH3-TPD(TPD:程序升温脱附)测得的NH3脱附量为10.0μmol/g以上。
另外,本发明涉及制造上述脱硝催化剂的制造方法,该制造方法包括在使上述基底含浸在溶解有五氧化二钒的螯合物溶液中之后进行烧制的工序。
另外,本发明涉及制造上述脱硝催化剂的制造方法,该制造方法包括在将溶解有五氧化二钒的螯合物溶液喷雾至所述基底之后进行烧制的工序。
发明的效果
本发明涉及的脱硝催化剂特别是在200℃以下的脱硝效率良好,能够将NO转化为无害的N2。另外,使用了本发明涉及的脱硝催化剂的选择性催化还原反应能够在200℃以下实施,因此不会伴随SO2的氧化。
附图说明
[图1]为由实施例1、参考例1~2、比较例1制备的五氧化二钒催化剂的X射线粉末衍射的结果。
[图2]为由实施例1~2、参考例3~6、比较例2~3制备的五氧化二钒催化剂的X射线粉末衍射的结果。
[图3]为表示由实施例1、参考例1~2、比较例1、比较例4制备的五氧化二钒催化剂的NH3-SCR活性的图。
[图4]为表示在使用由参考例1及比较例1制备的五氧化二钒催化剂的选择性催化还原反应中,反应温度与N2选择率的关系的图。
[图5]为表示在将由参考例1制备的五氧化二钒催化剂用于NH3-SCR反应时的空间速度依赖性的图。
[图6]为表示在将由参考例1制备的五氧化二钒催化剂用于水分共存下的选择性催化还原反应时的NO转化率的随时间经过的图。
[图7]为表示在将由参考例1制备的五氧化二钒催化剂用于S成分共存下的选择性催化还原反应时的NH3、NO、SO2浓度的随时间经过的图。
[图8]为表示在各反应温度下由各实施例制备的五氧化二钒催化剂的五氧化二钒负载量与NO转化率的关系的图。
[图9]为表示由各实施例、各参考例、及各比较例制备的五氧化二钒催化剂的BET比表面积与NO转化率的关系的图。
[图10]为由实施例4~6、参考例7~8制备的五氧化二钒催化剂的X射线粉末衍射的结果。
[图11]为表示由实施例4~6、参考例7~8制备的五氧化二钒催化剂的NH3-SCR活性的图。
[图12]为表示由实施例4~6、参考例1~2、参考例7、比较例1制备的五氧化二钒催化剂的比表面积与NO转化率的关系的图。
[图13]为表示由实施例4~5、参考例1~2、比较例1制备的五氧化二钒催化剂的BET比表面积与NH3脱附量的关系的图。
[图14]为表示由实施例4~5、参考例1~2、比较例1制备的五氧化二钒催化剂的NH3脱附量与NO转化率的关系的图。
具体实施方式
以下,针对本发明的实施方式进行说明。
本发明的脱硝催化剂是在基底上涂覆催化剂成分而成的脱硝催化剂,其中,上述催化剂成分中存在43wt%以上的五氧化二钒,上述催化剂成分的BET比表面积为30m2/g以上,该脱硝催化剂用于在200℃以下的脱硝。这样的脱硝催化剂与以往使用的钒/钛催化剂等脱硝催化剂相比,即使在低温环境下也能够发挥出高脱硝效果。
具体而言,在使用了存在以五氧化二钒换算计为3.3wt%以上的氧化钒的脱硝催化剂的、以氨为还原剂的选择性催化还原反应(NH3-SCR)中,大体而言,在反应温度为120℃的情况下,显示出约35%以上的NO转化率,在反应温度为150℃的情况下,显示出约60%以上的NO转化率。即使是在反应温度为100℃的情况下,也显示出超过20%的NO转化率。另一方面,在脱硝催化剂中仅存在以五氧化二钒换算计小于3.3wt%的氧化钒的情况下,无论是在反应温度为120℃的情况下还是在反应温度为150℃的情况下,均仅显示出小于20%的NO转化率。
如上所述,在本发明涉及的脱硝催化剂中涂覆的催化剂成分中,存在以五氧化二钒换算计为43wt%以上的氧化钒,但除了氧化钒以外,还可以包含氧化钛作为其它含有物。此外,也可以包含贵金属及贱金属、典型金属。优选地,也可以包含氧化钨、氧化铬、氧化钼等。
另外,在上述记载中,提到了在催化剂成分中优选存在43wt%以上的五氧化二钒,但需要说明的是,优选地,在催化剂成分中也可以存在以五氧化二钒换算计为80wt%以上的氧化钒。进一步优选地,在催化剂成分中氧化钒也可以为100%。
上述氧化钒包括氧化钒(II)(VO)、三氧化二钒(III)(V2O3)、二氧化钒(IV)(V2O4)、五氧化二钒(V)(V2O5),在脱硝反应中,五氧化二钒(V2O5)的V元素可以取5价、4价、3价、2价的形态。
另外,关于催化剂成分的BET比表面积,例如,在使用了包含五氧化二钒且BET比表面积为13.5m2g-1的脱硝催化剂的、反应温度为120℃的NH3-SCR中,NO转化率大于20%。另外,在使用了包含五氧化二钒且BET比表面积为16.6m2g-1的脱硝催化剂的、反应温度为120℃的NH3-SCR中,NO转化率也大于20%。另一方面,在使用了作为BET比表面积小于10m2/g的脱硝催化剂的例如BET比表面积为4.68m2/g的脱硝催化剂的、反应温度为120℃的NH3-SCR中,NO转化率小于20%。
另外,催化剂成分的BET比表面积为30m2/g以上,但优选地,催化剂成分的BET比表面积也可以为40m2/g以上。进一步优选地,催化剂成分的BET比表面积也可以为50m2/g以上。进一步优选地,催化剂成分的BET比表面积也可以为60m2/g以上。
需要说明的是,催化剂成分的BET比表面积优选按照JIS Z8830:2013中规定的条件进行测定。具体而言,可以利用以下实施例中记载的方法来测定BET比表面积。
本发明的脱硝催化剂可用于在200℃以下的脱硝。优选用于在160℃以上且200℃以下的脱硝。由此,在NH3-SCR反应时不会伴随SO2向SO3的氧化。
关于利用NH3-TPD(TPD:程序升温脱附)测得的NH3脱附量,NH3脱附量大于10.0μmol/g的脱硝催化剂在反应温度为120℃时的NH3-SCR中的NO转化率显示为20%以上的值。另一方面,NH3脱附量小于10.0μmol/g的脱硝催化剂在反应温度为120℃时的NH3-SCR中的NO转化率小于20%。
本发明的催化剂成分的利用NH3-TPD(TPD:程序升温脱附)测得的NH3脱附量为10.0μmol/g以上,优选地,利用NH3-TPD测得的NH3脱附量也可以为20.0μmol/g以上。更优选地,利用NH3-TPD测得的NH3脱附量也可以为50.0μmol/g以上。进一步优选地,利用NH3-TPD测得的NH3脱附量也可以为70.0μmol/g以上。
存在43wt%以上的五氧化二钒且BET比表面积为30m2/g以上的脱硝催化剂的催化剂成分可利用热分解法、溶胶凝胶法及含浸法中的任意方法制作。以下,示出利用热分解法、溶胶凝胶法及含浸法来制作存在3.3wt%以上的五氧化二钒且BET比表面积为10m2/g以上的脱硝催化剂的方法。
热分解法包括将钒酸盐进行热分解的工序。作为钒酸盐,可使用例如钒酸铵、钒酸镁、钒酸锶、钒酸钡、钒酸锌、钒酸铅、钒酸锂等。
需要说明的是,上述热分解法中,优选于300℃~400℃将钒酸盐进行热分解。
溶胶凝胶法包括将钒酸盐溶解于螯合物并进行干燥之后进行烧制的工序。作为螯合物,可使用例如:草酸、柠檬酸等具有多个羧基的物质、乙酰丙酮化物、乙二胺等具有多个氨基的物质、乙二醇等具有多个羟基的物质等。
需要说明的是,虽然因螯合物而异,但上述溶胶凝胶法优选包括例如以使钒与螯合物的摩尔比成为1:1~1:5的方式将钒酸盐溶解于螯合物的工序。需要说明的是,优选地,钒酸盐与螯合物的摩尔比也可以为1:2~1:4。
含浸法包括下述工序:在将钒酸盐溶解于螯合物之后加入载体,之后进行干燥,然后进行烧制。作为载体,可使用氧化钛、氧化铝、二氧化硅等。与上述同样地,作为螯合物,可使用例如:草酸、柠檬酸等具有多个羧基的物质、乙酰丙酮化物、乙二胺等具有多个氨基的物质、乙二醇等具有多个羟基的物质等。
需要说明的是,在上述含浸法中,可以通过例如将钒酸铵溶解于草酸溶液、再加入作为载体的氧化钛(TiO2)之后进行干燥,然后进行烧制,由此得到作为本发明的实施方式所涉及的脱硝催化剂的xwt%V2O5/TiO2(x≥43)。
在这样制备的脱硝催化剂中,通常包含3.3wt%以上的五氧化二钒,且比表面积为10m2/g以上。
另外,上述脱硝催化剂基本上为粉末状,但正如日本特开2005-199108号公报中公开的那样,例如在设置于火电站的烟气脱硝装置中,有时使用在蜂窝形状的基底上涂覆催化剂成分而成的蜂窝型催化剂。本发明中,也可以在基底上涂覆上述脱硝催化剂作为催化剂成分。
具体而言,可以通过将基底浸渍于溶解有五氧化二钒的螯合物溶液中并干燥,然后进行烧制,从而制造在基底上涂覆有五氧化二钒的催化剂。或者,可以通过将溶解有五氧化二钒的螯合物溶液喷雾至基底并干燥,然后进行烧制,从而制造在基底上涂覆有五氧化二钒的催化剂。此处,与上述同样地,作为螯合物,可使用例如:草酸、柠檬酸等具有多个羧基的物质、乙酰丙酮化物、乙二胺等具有多个氨基的物质、乙二醇等具有多个羟基的物质等。
另外,五氧化二钒与螯合物的摩尔比优选为1:1~1:5。需要说明的是,优选地,五氧化二钒与螯合物的摩尔比也可以为1:2~1:4。另外,烧制温度优选在例如300℃左右。
另外,作为上述基底,只要在200℃以上的温度不会发生变形等,则可以使用任意基底。例如,作为基底,可以使用陶瓷、陶器、钛等金属。或者,也可以在新的催化剂或已使用过的催化剂上进一步涂覆本发明的催化剂成分。另外,基底可以形成为任意形状,例如,可以形成为板状、颗粒状、流体状、圆柱型、星型状、环状、挤出型、球状、薄片状、锭状(pastille)、肋条挤出状、波纹状(rippling)中的任意形状。
根据上述实施方式涉及的脱硝催化剂,可实现以下效果。
(1)如上所述,就上述实施方式涉及的脱硝催化剂而言,其是在基底上涂覆催化剂成分而成的脱硝催化剂,并且,上述催化剂成分中存在43wt%以上的五氧化二钒,上述催化剂成分的BET比表面积为30m2/g以上,上述脱硝催化剂用于在200℃以下的脱硝。
通过使用该脱硝催化剂,即使对于在200℃以下的选择性催化还原反应来说也能够发挥出高脱硝效果。
另外,在使用了上述实施方式涉及的脱硝催化剂的选择性催化还原反应中,不会导致SO2氧化,可带来高脱硝效果。
(2)如上所述,上述实施方式涉及的脱硝催化剂的催化剂成分的利用NH3-TPD(TPD:程序升温脱附)测得的NH3脱附量优选为10.0μmol/g以上。
由此,在反应温度为120℃的NH3-SCR中使用该脱硝催化剂时,显示出大于20%的NO转化率。
(3)如上所述,上述实施方式涉及的脱硝催化剂的制造方法优选包括使上述基底含浸在溶解有五氧化二钒的螯合物溶液中然后进行烧制的工序。
由此,上述实施方式涉及的脱硝催化剂的比表面积变大,使用了上述实施方式涉及的脱硝催化剂的选择性催化还原反应中的脱硝效果提高。
(4)如上所述,上述实施方式涉及的脱硝催化剂的制造方法优选包括将溶解有五氧化二钒的螯合物溶液喷雾至上述基底然后进行烧制的工序。
由此,上述实施方式涉及的脱硝催化剂的比表面积变大,使用了上述实施方式涉及的脱硝催化剂的选择性催化还原反应中的脱硝效果提高。
需要说明的是,本发明并不限定于上述实施方式,在能够实现本发明目的的范围内所作的变形、改良等包括在本发明中。
实施例
以下,结合参考例及比较例对本发明的催化剂成分的实施例进行具体说明。需要说明的是,本发明不受这些实施例的限定。
1.氧化钒含量及比表面积与NH3-SCR活性的关系
1.1各实施例和比较例
[参考例1]
将钒酸铵(NH4VO3)在空气中于300℃进行4小时热分解,将由此得到的五氧化二钒(V2O5)作为参考例1的脱硝催化剂。其中,将该参考例1的脱硝催化剂的样品名设为“V2O5_300”。
[参考例2]
将钒酸铵在空气中于400℃进行4小时热分解,将由此得到的五氧化二钒作为参考例2的脱硝催化剂。其中,将该参考例2的脱硝催化剂的样品名设为“V2O5_400”。
[比较例1]
将钒酸铵在空气中于500℃进行4小时热分解,将由此得到的五氧化二钒作为比较例1的脱硝催化剂。需要说明的是,将该比较例1的脱硝催化剂的样品名设为“V2O5_500”。
[实施例1]
使钒酸铵溶解于草酸溶液(钒:草酸的摩尔比=1:3)。完全溶解之后,在加热搅拌器上使溶液中的水分蒸发,在干燥机中于120℃干燥过夜。然后,将干燥后的粉末在空气中于300℃进行了4小时烧制。将烧制后的五氧化二钒作为实施例1的脱硝催化剂。需要说明的是,将该利用溶胶凝胶法得到的实施例1的脱硝催化剂的样品名设为“V2O5_SG_300”。另外,关于将钒酸铵溶解于草酸溶液时钒与草酸的摩尔比不同的脱硝催化剂,如后文所述。
[比较例2]
将钒酸铵加入草酸溶液中,搅拌10分钟,缓慢地加入作为载体的氧化钛。然后,在加热搅拌器上使溶液中的水分蒸发,在干燥机中于120℃干燥过夜。然后,将干燥后的粉末在空气中于300℃进行了4小时烧制。作为其结果,将五氧化二钒的质量百分比成为0.3wt%的烧制后的脱硝催化剂作为比较例2的脱硝催化剂。需要说明的是,将该比较例2的脱硝催化剂的样品名设为“0.3wt%V2O5/TiO2”。
[比较例3]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为0.9wt%的烧制后的脱硝催化剂作为比较例3的脱硝催化剂。需要说明的是,将该比较例3的脱硝催化剂的样品名设为“0.9wt%V2O5/TiO2”。
[参考例3]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为3.3wt%的烧制后的脱硝催化剂作为参考例3的脱硝催化剂。需要说明的是,将该参考例3的脱硝催化剂的样品名设为“3.3wt%V2O5/TiO2”。
[参考例4]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为9wt%的烧制后的脱硝催化剂作为参考例4的脱硝催化剂。需要说明的是,将该参考例4的脱硝催化剂的样品名设为“9wt%V2O5/TiO2”。
[参考例5]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为20wt%的烧制后的脱硝催化剂作为参考例5的脱硝催化剂。需要说明的是,将该参考例5的脱硝催化剂的样品名设为“20wt%V2O5/TiO2”。
[参考例6]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为33wt%的烧制后的脱硝催化剂作为参考例6的脱硝催化剂。需要说明的是,将该参考例6的脱硝催化剂的样品名设为“33wt%V2O5/TiO2”。
[实施例2]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为43wt%的烧制后的脱硝催化剂作为实施例2的脱硝催化剂。需要说明的是,将该实施例2的脱硝催化剂的样品名设为“43wt%V2O5/TiO2”。
[实施例3]
将利用与比较例2同样的方法得到、并且五氧化二钒的质量百分比为80wt%的烧制后的脱硝催化剂作为实施例3的脱硝催化剂。需要说明的是,将该实施例3的脱硝催化剂的样品名设为“80wt%V2O5/TiO2”。
[比较例4]
将现有催化剂作为比较例4。需要说明的是,所述现有催化剂,是指在氧化钛(TiO2)(含有率:79.67wt%)上负载有氧化钨(WO3)(含有率:10.72wt%)及二氧化硅(SiO2)(含有率:6.25wt%)等,且包含0.5%左右的钒的催化剂。
1.2评价
1.2.1X射线粉末衍射
(衍射方法)
作为X射线粉末衍射,利用Rigaku smart lab、使用Cu-Ka进行测定。
(衍射结果)
实施例1(V2O5_SG_300)、参考例1(V2O5_300)、参考例2(V2O5_400)、及比较例1(V2O5_500)的粉末XRD图谱如图1所示,实施例1(V2O5_SG_300)、实施例2、参考例3~6、及比较例2~3(xwt%V2O5/TiO2)的粉末XRD图谱如图2所示。在实施例1(V2O5_SG_300)、参考例1(V2O5_300)、参考例2(V2O5_400)、比较例1(V2O5_500)的粉末XRD图谱中,不论热分解温度、制备方法如何,均观察到仅V2O5的峰。关于实施例2、参考例3~6、及比较例2~3(xwt%V2O5/TiO2)的粉末XRD图谱,直到9wt%为止未观察到V2O5峰,可认为是高度分散在TiO2中。V2O5负载量增加到20wt%时,在22.2°、27.4°观察到了V2O5的峰,每当增大负载量就会使得V2O5峰强度增大。另一方面,TiO2峰存在减小的倾向。
1.2.2BET比表面积测定
(测定方法)
BET比表面积的测定使用了MicrotracBEL BELSORP-max。在Ar气氛下,于200℃进行了2小时前处理,然后于196℃进行测定。
(测定结果)
[表1]
五氧化二钒催化剂的BET比表面积
参考例1(V2O5_300)、参考例2(V2O5_400)、比较例1(V2O5_500)、实施例1(V2O5_SG_300)、和比较例2~3、参考例3~6、及实施例2~3(xwt%V2O5/TiO2催化剂)、及比较例4(现有催化剂)的BET比表面积如表1所示。对于通过将钒酸铵进行热分解而制备的五氧化二钒催化剂而言,随着热分解温度升高,BET比表面积减少。即,对于显示出最大BET比表面积的五氧化二钒而言,在于300℃发生了热分解的参考例1(V2O5_300)的五氧化二钒中,显示出了最大的BET比表面积16.6m2g-1。另外,利用溶胶凝胶法于300℃制成的五氧化二钒的BET比表面积更大,为62.9m2g-1。
关于参考例3~6、及实施例2~3、及比较例2~3(xwt%V2O5/TiO2),随着五氧化二钒的负载量的增加,TiO2的细孔被掩埋,BET比表面积降低。
1.2.3催化活性测定
(测定方法)
在下述表2的条件下,使用固定床流通式催化剂反应装置进行NH3-SCR反应。利用Jasco FT-IR-4700,对从催化剂层中通过的气体中的NO、NH3、NO2、N2O进行分析。
[表2]
NH3-SCR测定条件
另外,利用下式计算出NO转化率、N2选择率。需要说明的是,NOin是反应管入口的NO浓度,NOout是反应管出口的NO浓度,N2out是反应管出口的N2浓度,NH3in是反应管入口的NH3浓度,NH3out是反应管出口的NH3浓度。
[数学式1]
[数学式2]
(2*N2out=(NOin+NH3in)-(NOout+NH3out+NO2out+2*N2Oout))
(测定结果)
图3示出五氧化二钒催化剂的NH3-SCR活性。在为将钒酸铵进行热分解而得到的催化剂的情况下,随着热分解温度降低,NO转化率增大,作为热分解温度为300℃的催化剂的参考例1(V2O5_300℃)显示出最高的活性。另外,在反应温度为200℃的条件下,将参考例1(V2O5_300℃)、参考例2(V2O5_400℃)、实施例1(V2O5_SG_300℃)中的任一者用作催化剂时,均有80%以上的NO转化率。此外,与比较例1及比较例4相比,任意实施例均显示出更高的NO转化率。
热分解温度越低,五氧化二钒的比表面积越大,因此,认为使用了块状(bulk)五氧化二钒催化剂的低温NH3-SCR活性归因于BET比表面积的大小。因此,如上所述,作为实施例1,为了增大BET比表面积而采用了使用草酸的溶胶凝胶法来制备五氧化二钒。利用该方法制备的五氧化二钒的BET比表面积如表1中记载的那样,为62.9m2g-1,其具有利用热分解法制备的五氧化二钒的约近4倍的大小。与利用热分解法制备的五氧化二钒相比,实施例1(V2O5_SG_300℃)的NO转化率在100-150℃间上升了80-200%。
需要说明的是,在任意温度下,N2选择率基本上均为100%。在图4中,作为例子而示出了参考例1(V2O5_300℃)和比较例1(V2O5_500℃)的N2选择率。
(空间速度依赖性)
在下述表3的条件下,进行选择性催化还原反应,由此测定将参考例1(V2O5_300℃)用作催化剂时的空间速度(气体处理用)依赖性。测定结果如图5所示。图5(a)示出反应温度120℃时的NO转化率,图5(b)示出反应温度100℃时的NO转化率。
对于80%的NO无害化的实现而言,120℃时约为15Lh-1gcat-1,100℃时约为11Lh- 1gcat -1。
在改变空间速度的实验中,向N2的选择率也基本上为100%。
[表3]
NH3-SCR测定条件
(水分共存下的反应)
将参考例1(V2O5_300℃)作为催化剂,将在以下表4的条件下以150℃的反应温度、20Lh-1gcat -1的空间速度进行NH3-SCR反应的实验时的、伴随时间经过的NO转化率示于图6。自反应开始经过1.5小时后添加2.3%的H2O,结果NO转化率由64%下降至50%。即使添加了H2O,向N2的选择性仍然未发生变化,为100%。自反应开始经过3.5小时后停止导入水,结果NO转化率增加,成为67%。
[表4]
NH3·SCR测定条件
(S成分共存下的反应)
在与上述水分共存下的反应所涉及的实验相同的条件下,在反应气体中流通100ppm的SO2。实验结果如图7所示。NO的催化活性未发生变化,虽然从直至150℃的温度上升结束后起,始终存在H2O和O2,但SO2的浓度并未降低,SO2未发生反应。由此可知,实施例的脱硝催化剂还具有耐S性。
(五氧化二钒负载量与NO转化率的关系)
图8示出了在各反应温度下五氧化二钒负载量与NO转化率的关系。图8(a)示出了反应温度为120℃时的五氧化二钒负载量与NO转化率的关系。同样地,图8(b)示出了反应温度为150℃时的五氧化二钒负载量与NO转化率的关系,图8(c)示出了反应温度为100℃时的五氧化二钒负载量与NO转化率的关系。需要说明的是,在各图中,五氧化二钒负载量成为100wt%的催化剂为上述实施例1中制备的脱硝催化剂V2O5_SG_300。使用四边形进行描绘的点表示作为比较例4的现有催化剂的NO转化率。
在全部的图中,大体上显示出:五氧化二钒负载量越增加,NO转化率越提高。但是,在任意图中,五氧化二钒负载量为3.3wt%的催化剂均显示出比五氧化二钒负载量为9.0wt%的催化剂更高的NO转化率。
具体而言,如在图8(a)中观察到的,在反应温度120℃的NH3-SCR反应中,在五氧化二钒负载量成为80wt%的阶段,NO转化率成为80%。另外,如在图8(b)中观察到的,在反应温度150℃的NH3-SCR反应中,在五氧化二钒负载量成为3.3wt%的阶段,显示出NO转化率大幅上升。此外,如在图8(c)中所观察到的,在反应温度为100℃的选择性催化还原反应中,与五氧化二钒负载量为43wt%以下的脱硝催化剂相比,采用五氧化二钒负载量为80wt%的脱硝催化剂时,显示出NO转化率大幅提高。
(BET比表面积与NO转化率的关系)
图9(a)示出了将五氧化二钒负载于氧化钛而成的脱硝催化剂的、BET比表面积与NO转化率的关系。在将五氧化二钒负载于氧化钛而成的脱硝催化剂中,随着负载量增加,一般而言会显示出:BET比表面积减少,但另一方面活性增高。
另外,图9(b)示出了将五氧化二钒负载于氧化钛而成的脱硝催化剂、和未负载于氧化钛的脱硝催化剂这两者的BET比表面积与NO转化率的关系。在未使五氧化二钒负载于氧化钛的催化剂中,显示出BET比表面积越增大,活性越增高。
2.利用溶胶凝胶法制造的V2O5催化剂
2.1各实施例(实施例4~6、参考例7~8)
在上述的“1.1各实施例和比较例”中,作为“实施例1”,以使钒与草酸的摩尔比成为1:3的方式使钒酸铵溶解于草酸溶液之后使水分蒸发进行干燥,对干燥粉末进行烧制,制作脱硝催化剂。将使该钒与草酸的摩尔比为1:1、1:2、1:3、1:4、1:5的脱硝催化剂作为参考例7、实施例4~6、参考例8。
具体而言,如上所述,使钒酸铵溶解于草酸溶液(钒:草酸的摩尔比=1:1~1:5)。完全溶解之后,在加热搅拌器上使溶液中的水分蒸发,并在干燥机中于120℃干燥过夜。然后,将干燥后的粉末在空气中于300℃进行4小时烧制。
将它们的样品名分别设为“V2O5_SG_1:1”(参考例7)、“V2O5_SG_1:2”(实施例4)、“V2O5_SG_1:3”(实施例5)、“V2O5_SG_1:4”(实施例6)、“V2O5_SG_1:5”(参考例8)。
需要说明的是,“1.1各实施例和比较例”中的“实施例1”的“V2O5_SG_300”与实施例5的“V2O5_SG_1:3”实质上为同一物质,但为了便于说明,在此,记载为样品名为“V2O5_SG_1:3”的“实施例5”。
需要说明的是,为了提高BET比表面积,也可以向草酸溶液中加入表面活性剂。作为表面活性剂,可示例例如:十六烷基三甲基溴化铵(CTAB)、十二烷基硫酸钠(SDS)、十六烷基胺等阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂、非离子表面活性剂。
2.2评价
2.2.1X射线粉末衍射
(衍射方法)
与上述1.2.1同样地,X射线粉末衍射通过Rigaku smart lab并使用Cu-Ka进行测定。
(衍射结果)
参考例7、实施例4~6、参考例8(V2O5_SG)的粉末XRD图谱如图10所示。对于使用钒:草酸比为1:1、1:2、1:5的溶液制作的五氧化二钒(参考例7、7及10)而言,仅检测到了斜方晶V2O5峰,但在使用钒:草酸比为1:3、1:4的溶液制作的五氧化二钒(实施例5及6)中,除了斜方晶V2O5峰以外,还在11°检测到了未确认峰。然而,目前尚无法鉴定。
2.2.2BET比表面积测定
(测定方法)
与上述1.2.3同样地,BET比表面积的测定使用了MicrotracBEL BELSORP-max。在Ar气氛下,于200℃进行了2小时前处理,然后于196℃进行测定。
(测定结果)
[表5]
五氧化二钒催化剂的BET比表面积
参考例7(V2O5_SG_1:1)、实施例4(V2O5_SG_1:2)、实施例5(V2O5_SG_1:3)、实施例6(V2O5_SG_1:4)、参考例8(V2O5_SG_1:5)的BET比表面积如表5所示。随着草酸比率增高,比表面积增加,直到钒:草酸比达到1:3为止,在该比例以上时比表面积减少。另外,与催化活性试验之前相比,以下的催化活性试验后的实施例5(V2O5_SG_1:3)的比表面积大幅减少,为43.4m2g-1。
2.2.3催化活性测定
(测定方法)
利用与上述1.2.4相同的测定方法测定各V2O5_SG催化剂的NH3-SCR活性,并计算出NO转化率。
(测定结果)
图11示出V2O5_SG催化剂的NH3-SCR活性。图11(a)示出在使用各催化剂的NH3-SCR反应中的各反应温度的NO转化率。另外,图11(b)示出在反应温度120℃时钒:草酸的比率与NO转化率的关系。在作为钒:草酸的比率为1:3的催化剂的实施例5(V2O5_SG_1:3)中,NO转化率最高,而进一步加入草酸时,NO转化率减少。与实施例4(V2O5_SG_1:2)相比,实施例6(V2O5_SG_1:4)虽然比表面积更大,但NO转化率降低。
(比表面积与NO转化率的关系)
图12示出了实施例4~6、参考例7的各V2O5_SG、以及上述参考例1(V2O5_300)、参考例2(V2O5_400)、比较例1(V2O5_500)中的BET比表面积与NO转化率的关系。需要说明的是,以四边形的点表示的图标示出了实施例5(V2O5_SG_1:3)的、选择性催化还原反应后的BET比表面积与NO转化率的关系。如上所述,就作为钒:草酸的比率为1:3的催化剂的实施例5(V2O5_SG_1:3)而言,显示出NO转化率最高。
2.2.4利用NH3-TPD进行的表征(characterization)
(测定方法)
利用NH3-TPD(TPD:程序升温脱附),可以估算催化剂表面的酸性位点的量。于是,使用MicrotracBEL公司制的BELCAT,在装置中,在He(50ml/min)流通下,于300℃对参考例1(V2O5_300)、参考例2(V2O5_400)、比较例1(V2O5_500)、实施例4(V2O5_SG_1:2)、实施例5(V2O5_SG_1:3)的各催化剂0.1g进行1小时前处理。然后,降至100℃,使5%氨/He(50ml/min)流通30分钟,对氨进行吸附。将流通气体切换为He(50ml/min),进行30分钟的稳定化之后,以10℃/min进行升温,利用质谱仪对质量数为16的氨进行监测。
(测定结果)
[表6]
利用NH3-TPD测得的NH3脱附量
分别使用参考例1(V2O5_300)、参考例2(V2O5_400)、比较例1(V2O5_500)、实施例4(V2O5_SG_1:2)、实施例5(V2O5_SG_1:3)时的NH3脱附量的测定结果示于表6。
对这些NH3脱附量的值与各催化剂的BET比表面积进行绘图,得到了图13的图。由该图13的图也可知,显示出NH3脱附量与V2O5的BET比表面积大致成比例地增大。另外,对各催化剂的NH3脱附量与NO转化率的对应关系进行绘图,得到了图14的图。即,显示出:NH3脱附量(=催化剂表面的酸性位点的量)越大的催化剂,其NO转化率越高。
如上所述,在使用了存在以五氧化二钒换算计为3.3wt%以上的氧化钒、且比表面积为10m2/g以上的本发明的脱硝催化剂的、以氨为还原剂的选择性催化还原反应中,200℃以下的低温时的脱硝效率高。另一方面,未确认到SO2的氧化。
Claims (2)
1.脱硝催化剂,其是在载体上负载五氧化二钒而成的脱硝催化剂,
其中,存在43wt%以上的所述五氧化二钒,BET比表面积为30m2/g以上,所述脱硝催化剂用于在200℃以下的脱硝。
2.权利要求1所述的脱硝催化剂的制造方法,其包括下述工序:
向钒酸盐溶解于螯合物的溶液而成的液体中加入所述载体并干燥,然后进行烧制。
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