CN109999891A - 一种低温scr脱硝催化剂及其制备方法 - Google Patents
一种低温scr脱硝催化剂及其制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004411 aluminium Substances 0.000 claims abstract description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 35
- 238000001354 calcination Methods 0.000 claims description 34
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- 238000000034 method Methods 0.000 claims description 25
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
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- 239000000843 powder Substances 0.000 claims description 6
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- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
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- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
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- 150000002697 manganese compounds Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003438 strontium compounds Chemical class 0.000 claims description 2
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- 230000003647 oxidation Effects 0.000 claims 1
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 36
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- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 description 2
- 101100456282 Caenorhabditis elegans mcm-4 gene Proteins 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01D53/8625—Nitrogen oxides
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Abstract
本发明公开了一种低温SCR脱硝催化剂及制备方法。该催化剂包括载体以及负载在该载体上的活性组分和掺杂改性组分,其中载体为MCM‑41或锶或锆或铝掺杂改性的MCM‑41,所述活性组分为锰。本发明采用等体积浸渍发制备的催化剂具有介孔有序结构,制备工艺简单易行,具有良好的应用前景,其中Mn/Al‑MCM‑41在180~400℃宽温度窗口中保持优异的SCR脱硝活性,氮氧化物去除率达60%以上,200~400℃维持100%的氮氧化物去除率。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种低温SCR脱硝催化剂及其制备方法。
背景技术
氮氧化物是大气的主要污染物之一,大气中的氮氧化物重要来源于火电厂以及汽车尾气等,其大量排放会造成酸雨和光化学烟雾等。严重危害人类健康及动植物生长。因此,如何有效去除氮氧化物成为当今的研究热点。
在众多的脱硝技术中,NH3-SCR是最有效的一种方法,核心是催化剂的选择。目前,商业化的催化剂是V2O5-WO3-TiO2催化剂。该催化剂活性温度窗口窄(300-400℃),钒的毒性以及易发生二氧化硫氧化等因素限制了该催化剂的使用,因此开发出新型的SCR活性较高且环境友好的催化剂是当前急需解决的问题。
现有技术公开一种W、Mn和Ce改性V-MCM-41/堇青石催化剂,在300℃时,NO的去除效率为20%左右,380℃能实现80%的NO去除效率。该催化剂在较高温度(>350℃)对NO有较好的去除率。但是在低温条件下对NO的去除率急剧下降,严重制约了催化剂的应用。
发明内容
针对上述现有技术,本发明提供一种低温SCR脱硝催化剂,以解决现有脱硝催化剂在低温条件下脱硝效果差的问题。
为了达到上述目的,本发明所采用的技术方案是:提供一种低温SCR脱硝催化剂,催化剂包括载体以及负载于载体上的活性组分和改性组分;载体为MCM-41,活性组分为含锰化合物,改性组分为含锶化合物、含锆化合物或含铝化合物,且催化剂中锰的质量百分比为3%~7%(催化剂中锰元素所占的质量百分比),锶、锆或铝的质量百分比1%~4%(催化剂中锶、锆或铝元素所占的质量百分比)。
在上述技术方案的基础上,本发明还可以做如下改进。
进一步,活性组分为二氧化锰,且催化剂中锰的质量百分比为5%。
进一步,改性组分为氧化锶、氧化锆或氧化铝,且催化剂中锶、锆或铝的质量百分比为2%。
本发明中的低温SCR脱硝催化剂经过以下步骤制得:
S1:取改性前体,将其配成浓度为0.02~0.50g/ml的改性溶液,然后将MCM-41以1g:0.5~2ml的料液比加入到改性溶液中,再搅拌15min,然后于100℃~120℃条件下烘干,得产物一;所述改性前体为Sr(NO3)2、Al(NO3)3·9H2O或Zr(NO3)4·5H2O;
S2:将产物一于480~520℃下煅烧2~4h,得煅烧产物;
S3:取活性前体,将其配成浓度为0.02~0.50g/ml的改性溶液,再将S2中得到的煅烧产物以1g:1ml的料液比加入到改性溶液中,再搅拌15min,然后于100℃~120℃条件下烘干,得产物二;所述活性前体为硝酸锰;
S4:将产物二于400~600℃下煅烧2~3h,得低温SCR脱硝催化剂。
为提升催化剂的品质,在制备时可以做如下进一步优化:
进一步,S1中MCM-41与改性溶液的料液比为1g:1ml,烘干温度为110℃。
进一步,S2中煅烧温度为500℃,煅烧时间为3h。
进一步,S4中煅烧温度为500℃,煅烧时间为3h。
进一步,S1中所用MCM-41经过以下步骤制得:
(1):将十六烷基三甲基溴化铵溶于水中并调节溶液的pH值为11~13,然后向溶液中加入正硅酸乙酯,搅拌均匀得混合液;混合液于60℃水浴下搅拌反应2h,得悬浊液;混合液中十六烷基三甲基溴化铵、正硅酸乙酯与水的摩尔比为0.1~0.5:1~2:70;
(2):将悬浊液转移至聚四氟乙烯反应釜中,于130℃下反应24h,然后降至室温并抽滤,用去离子水将沉淀清洗至中性,110℃下烘干得白色粉末;
(3):对步骤二所得到的白色粉末进行煅烧,得到有序介孔材料MCM-41。
其中,步骤(1)最好调节十六烷基三甲基溴化铵溶液的pH值为12;混合液中十六烷基三甲基溴化铵、正硅酸乙酯和水的最优摩尔比为0.1:1:70。
步骤(3)中煅烧分两段进行,第一段煅烧温度为360℃,煅烧时间为1h;第二段煅烧温度为550℃,煅烧时间为6h。
本发明的有益效果是:
1.制备工艺简单、对设备的要求较低。
2.本发明所制备的MCM-41孔道结构规整、孔径分布较窄(1.5~10nm),并具有较大的孔容积(孔容高于0.7cm3/g)和较高的比表面积(比表面积可达1000m2/g),而且表面酸强度适中、热稳定性较好,以其为载体制得的催化剂稳定性好,催化效率高,能有效去除废气中的氮氧化物。
3.通过少量的掺杂改性组分可以调变分子筛MCM-41的酸碱性,从而改变反应物在催化剂上的吸附并被活化;另外,掺杂改性组分具有一定的电子助剂和结构助剂的作用,能够影响活性组分Mn在载体上的电子特性和分散性,从而有效提高了催化剂的脱硝性能,拓宽催化剂的活性温度窗口,在180-400℃的宽温度范围内,氮氧化物的净化效率达60%以上,200-400℃维持100%的氮氧化物去除率。
附图说明
图1为不同Mn负载量下xMn/MCM-41的小角度XRD图;
图2为不同Mn负载量下xMn/MCM-41的全扫描XRD图;
图3为Sr、Al或Zr改性的MCM-41负载Mn后的Mn/M-MCM-41小角度XRD图;
图4为Sr、Al或Zr改性的MCM-41负载Mn后的Mn/M-MCM-41全扫描XRD图;
图5为不同Mn负载量下xMn/MCM-41的SCR活性图;
图6为Sr、Al或Zr改性的MCM-41负载Mn后的Mn/M-MCM-41的SCR活性图;
图7为不同铝掺杂量下的SCR活性图。
具体实施方式
下面结合实施例对本发明的具体实施方式做详细的说明。
实施例1:制备载体MCM-41
将4.56g(0.0125mol)十六烷基三甲基溴化铵(CTAB)溶于158ml(约为8.75mol)蒸馏水中,用乙二胺调节pH值为12,然后加入26.04g(0.125mol)正硅酸乙酯(TEOS),在60℃水浴下搅拌2h,得到乳白色悬浊液;然后将得到的悬浊液转移至聚四氟乙烯反应釜中,于130℃下反应24h,自然降温后取出抽滤,得到的沉淀初始物用去离子水洗涤至中性,110℃下烘干过夜,得到白色粉末;再将得到的白色粉末在360℃下煅烧1小时,然后升温至550℃下煅烧6h,得到有序介孔材料MCM-41,即本发明中的载体。
下面利用制得的载体制备不同的催化剂。
实施例2
取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2g MCM-41,搅拌15min,完成浸渍过程;然后于110℃下烘干过夜;将产物于400℃煅烧3h,得到产物一,记为7Mn/MCM-41。
实施例3
取0.4025g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2g MCM-41,搅拌15min,完成浸渍过程,然后于100℃下烘干过夜;将产物500℃煅烧4h,得到产物二,记为3Mn/MCM-41。
实施例4
取0.6850g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2g MCM-41,搅拌15min,完成浸渍过程,然后于120℃下烘干过夜;将产物600℃煅烧2h,得到产物三,记为5Mn/MCM-41。
实施例5
取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2g MCM-41,搅拌15min,完成浸渍过程,然后于110℃下烘干过夜;将产物500℃煅烧3h,得到产物四,记为7Mn/MCM-41。
实施例6
取0.0488g的硝酸锶,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2gMCM-41,搅拌15min,完成浸渍过程,然后于110℃下烘干过夜;将产物500℃煅烧3h后,得到产物Sr-MCM-41;取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,加入2g Sr-MCM-41,搅拌15min,完成浸渍过程,然后于110℃下烘干过夜;将产物500℃煅烧3h,得到产物五,记为Mn/Sr-MCM-41。
实施例7
取0.2807g的硝酸铝,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2gMCM-41,搅拌15min,完成浸渍过程,然后于100℃下烘干过夜;将产物500℃煅烧3h后,得到产物Al-MCM-41;取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,加入2g Al-MCM-41,搅拌15min,完成浸渍过程,然后于100℃下烘干过夜;将产物500℃煅烧3h,得到产物六,记为Mn/Al-MCM-41。
实施例8
取0.0951g的硝酸锆,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2gMCM-41,搅拌15min,完成浸渍过程,然后于120℃下烘干过夜;将产物520℃煅烧2h后,得到产物Zr-MCM-41;取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,加入2g Zr-MCM-41,搅拌15min,完成浸渍过程,然后于120℃下烘干过夜;将产物400℃煅烧3小时,得到产物七,记为Mn/Zr-MCM-41。
实施例9
取0.8594g的硝酸铝,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2gMCM-41,搅拌15min,完成浸渍过程,然后于110℃下烘干过夜;将产物480℃煅烧4h后,得到产物Al-MCM-41;取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,加入2g Al-MCM-41,搅拌15min,完成浸渍过程,然后于100℃下烘干过夜;将产物600℃煅烧2h,得到产物六,记为Mn/3Al-MCM-41。
实施例10
取0.5671g的硝酸铝,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2gMCM-41,搅拌15min,完成浸渍过程,然后于110℃下烘干过夜;将产物500℃煅烧3h后,得到产物Al-MCM-41;取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,加入2g Al-MCM-41,搅拌15min,完成浸渍过程,然后于100℃下烘干过夜;将产物500℃煅烧3h,得到产物六,记为Mn/2Al-MCM-41。
实施例11
取1.1578g的硝酸铝,加入2ml蒸馏水搅拌均匀,配成水溶液;向水溶液中加入2gMCM-41,搅拌15min,完成浸渍过程,然后于110℃下烘干过夜;将产物500℃煅烧3h后,得到产物Al-MCM-41;取0.9796g的50%硝酸锰,加入2ml蒸馏水搅拌均匀,加入2g Al-MCM-41,搅拌15min,完成浸渍过程,然后于100℃下烘干过夜;将产物500℃煅烧3h,得到产物六,记为Mn/4Al-MCM-41。
结果分析
对不同负载量下的xMn/MCM-4进行XRD小角度扫描,结果如图1所示。从图中可以看出,各试样在2θ为2.2°左右均具有一个最强的衍射峰,对应MCM-41(100晶面),2θ=3.7°左右和4.3°左右有两个强度较弱的衍射峰,对应MCM-41的(110)和(200)晶面,表明制备的试样为六方有序介孔结构。
然后对不同锰负载量下的xMn/MCM-41进行XRD全扫描,结果如图2所示。可以看出,2θ=10~80°有一个大的弥散峰,说明试样均为无定形SiO2结构,活性组分锰被高度分散在载体表面。
对不同金属改性载体负载锰的Mn/M-MCM-41进行XRD小角度扫描,结果如图3所示。可以看出,不同金属改性载体后的XRD均出现了(100)(110)(200)晶面的峰,说明掺杂改性的金属并未破坏MCM-41的六方介孔结构。
对不同金属改性载体负载锰的Mn/M-MCM-41进行XRD全扫描,结果如图4所示。可以看出,图中只有一个大的弥散峰,说明引入不同金属改性的MCM-41仍以无定形的形态存在,而掺杂改性组分和活性组分锰均高度分散在分子筛表面。
检测负载有不同量的活性组分的催化剂的SCR脱硝性能,SCR脱硝性能以固定床装置测试,反应管内径14mm,测试条件为:NO=500ppm,NH3=500ppm,O2=5%,N2作为平衡气。总气量为500ml/min,空速30000h-1.。气体组分采用武汉四方光电科技有限公司Gasboard-3000烟气分析仪进行分析。转化率采用如下公式计算:
结果如图5所示。可以看出,温度为140~320℃区间,Mn/MCM-41,400℃焙烧3小时,活性组分负载量为7%的催化剂在200~320℃保持80%以上的转化率。3个催化剂在220℃以上氮氧化物转化率均高于50%。说明活性组分锰负载在MCM-41介孔分子筛上能表现出较好的脱硝性能。
图6为Sr、Al或Zr改性的MCM-41分子筛后负载活性组分Mn所制备的催化剂的SCR活性图。结果发现掺杂元素铝或锶或锆对Mn/MCM-41在200℃以下脱硝活性都有明显提高;在200℃时,氮氧化物去除率接近100%。其中,引入铝元素可以极大的提高SCR活性,所得催化剂在180-400℃保持优异的SCR活性,氮氧化物去除率达60%以上,200~400℃维持100%的氮氧化物去除率。
图7为不同铝掺杂量下的SCR活性图,负载不同量的改性组分铝都极大的扩宽了催化剂的工作窗口,200-400℃维持100%的氮氧化物去除率。
虽然结合实施例对本发明的具体实施方式进行了详细地描述,但不应理解为对本专利的保护范围的限定。在权利要求书所描述的范围内,本领域技术人员不经创造性劳动即可作出的各种修改和变形仍属本专利的保护范围。
Claims (10)
1.一种低温SCR脱硝催化剂,其特征在于:所述催化剂包括载体以及负载于所述载体上的活性组分和改性组分;所述载体为MCM-41,所述活性组分为含锰化合物,所述改性组分为含锶化合物、含锆化合物或含铝化合物,且所述催化剂中锰的质量百分比为3%~7%,锶、锆或铝的质量百分比1%~4%。
2.根据权利要求1所述的低温SCR脱硝催化剂,其特征在于:所述活性组分为二氧化锰,且催化剂中锰的质量百分比为5%。
3.根据权利要求要求1所述的低温SCR脱硝催化剂,其特征在于:所述改性组分为氧化锶、氧化锆或氧化铝,且催化剂中锶、锆或铝的质量百分比为2%。
4.制备如权利要求1~3任一项所述低温SCR脱硝催化剂的方法,其特征在于,包括以下步骤:
S1:取改性前体,将其配成浓度为0.02~0.50g/ml的改性溶液,然后将MCM-41以1g:0.5~2ml的料液比加入到改性溶液中,再搅拌15min,然后于100℃~120℃条件下烘干,得产物一;所述改性前体为Sr(NO3)2、Al(NO3)3·9H2O或Zr(NO3)4·5H2O;
S2:将产物一于480~520℃下煅烧2~4h,得煅烧产物;
S3:取活性前体,将其配成浓度为0.02~0.50g/ml的改性溶液,再将S2中得到的煅烧产物以1g:1ml的料液比加入到改性溶液中,再搅拌15min,然后于100℃~120℃条件下烘干,得产物二;所述活性前体为硝酸锰;
S4:将产物二于400~600℃下煅烧2~3h,得低温SCR脱硝催化剂。
5.根据权利要求4所述的方法,其特征在于:S1中MCM-41与改性溶液的料液比为1g:1ml,烘干温度为110℃。
6.根据权利要求4所述的方法,其特征在于:S2中煅烧温度为500℃,煅烧时间为3h。
7.根据权利要求4所述的方法,其特征在于:S4中煅烧温度为500℃,煅烧时间为3h。
8.根据权利要求4或5所述的方法,其特征在在于,所述MCM-41经过以下步骤制得:
(1):将十六烷基三甲基溴化铵溶于水中并调节溶液的pH值为11~13,然后向溶液中加入正硅酸乙酯,搅拌均匀得混合液;混合液于60℃水浴下搅拌反应2h,得悬浊液;混合液中十六烷基三甲基溴化铵、正硅酸乙酯与水的摩尔比为0.1~0.5:1~2:70;
(2):将悬浊液转移至聚四氟乙烯反应釜中,于130℃下反应24h,然后降至室温并抽滤,用去离子水将沉淀清洗至中性,110℃下烘干得白色粉末;
(3):对步骤二所得到的白色粉末进行煅烧,得到有序介孔材料MCM-41。
9.根据权利要求8所述的方法,其特征在于:步骤(1)调节十六烷基三甲基溴化铵溶液的pH值为12;混合液中十六烷基三甲基溴化铵、正硅酸乙酯和水的摩尔比为0.1:1:70。
10.根据权利要求8所述的方法,其特征在于:步骤(3)中煅烧分两段进行,第一段煅烧温度为360℃,煅烧时间为1h;第二段煅烧温度为550℃,煅烧时间为6h。
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CN113398978B (zh) * | 2021-06-28 | 2023-05-05 | 中国石油化工股份有限公司 | 一种邻氯环己酮及其催化剂的制备方法 |
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