CN109647504A - 一种用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂 - Google Patents
一种用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂 Download PDFInfo
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- CN109647504A CN109647504A CN201910096987.4A CN201910096987A CN109647504A CN 109647504 A CN109647504 A CN 109647504A CN 201910096987 A CN201910096987 A CN 201910096987A CN 109647504 A CN109647504 A CN 109647504A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 55
- 239000011032 tourmaline Substances 0.000 title claims abstract description 55
- 229940070527 tourmaline Drugs 0.000 title claims abstract description 55
- 239000004568 cement Substances 0.000 title claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 8
- 239000011941 photocatalyst Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- -1 manganese salt Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010457 zeolite Substances 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000007789 gas Substances 0.000 description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical group [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 10
- 239000003546 flue gas Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 7
- 229910016978 MnOx Inorganic materials 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910002551 Fe-Mn Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000002631 hypothermal effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Abstract
本发明为一种用于水泥窑含电气石的Mn,Fe,Ce/Cu‑SAPO‑34低温脱硝催化剂。该催化剂包括载体、助剂和活性组分;所述的载体为Cu‑SAPO‑34分子筛,助剂为铈元素和电气石,活性组分为锰盐和铁盐;其中,SAPO‑34分子筛来源于含模板剂的分子筛合成浆料;锰元素负载量为5~20%wt,铁元素负载量为1~10%wt,铈元素负载量为0.1%~1.0%wt;铜元素的负载量为1.0~3.0%wt,电气石的负载量为0.1%~3%wt。本发明克服了现有技术中低温SCR脱硝催化剂低温活性不好、工艺复杂、制备成本高和抗硫和抗水能力较低等缺点。
Description
技术领域
本文涉及低温烟气脱硝领域,具体为用于NH3选择性催化还原NO的一种含电气石的具有高抗硫耐水性能的铁锰低温脱硝催化剂及其制备方法。
背景技术
我国是水泥生产大国,2017年年产量达23.16亿吨。然而水泥生产过程中会产生大量的氮氧化物,随着我国电力行业逐步实现超低排放,包括水泥行业在内的非电行业已经成为下一阶段大气污染治理的重点。SCR烟气脱硝技术在火电行业已经非常成熟,但是水泥行业SCR烟气脱硝很大程度上还处在试验、个别项目示范和积累试验数据和运行经验的阶段,还缺乏工程应用的经验。随着我国对水泥行业排放要求的进一步提高,一些地方提出要实现小于150mg/m3甚至100mg/m3的NOx排放标准,以目前的技术手段,除SCR以外的脱硝技术难以实现,即便采用SCR烟气脱技术,还有一些技术和工程应用问题需要进一步的研究与解决。例如水泥窑烟气中含有大量的粉尘、水汽和二氧化硫等杂质,为了避免催化剂中毒,脱硝装置一般位于脱尘脱硫装置以后,但此时烟气温度已经低于商用催化剂活性温度窗口,需要额外加热,为了节能环保的要求,亟待开发用于水泥窑的低温SCR脱硝技术。
催化剂是低温SCR脱硝技术的核心,过渡金属氧化物是当今世界上研究最多的低温脱硝催化剂,铈、铁、铬、锰等金属氧化物以及其复合氧化物是目前研究的重点。从已有的研究结果来看,相对于其它过渡金属,铁锰催化剂在低温SCR领域显示出优越的性能。Ce元素作为丰富的储氧组分不仅可以作为催化剂的载体,也可以作为掺杂组分存在。Ce元素的价态可以在+4与+3价之间转变,在转变过程中会形成大量的空位缺陷,其次Ce离子的离子半径为0.1034nm,可以进入MnOx的空位中与其形成固溶体,进而改变MnOx的晶格常数,以上空位和固溶体的形成均会对催化效率产生影响。近些年来,具有CHA结构的Cu离子交换型分子筛催化剂由于其比表面积大、孔径均一、表面易修饰、优良的水热稳定性成为新的研究热点,如:Cu-SSZ-13和Cu-SAPO-34。Cu-SAPO-34因具有较高的NOx转化率和N2选择性、较宽的活性温窗、较强的水热稳定性而引起选择性催化还原(SCR)催化剂研究者的关注。但Cu-SAPO-34材料的低温催化活性不佳,而且常规制备过程包括分子筛合成、离子交换、涂覆以及多次焙烧,制备成本高,限制了其大规模使用。电气石是一种天然极性硅酸盐晶体矿物具有压电性、电热性、电极性等特点,具有强表面电场和良好的吸附性,能有效促进光生电子的激发转移,抑制电子-空穴的复合,增强催化剂的活性、拓展光谱响应范围,是作为催化剂载体的优良选择。本课题想借助电气石矿物与过渡金属催化剂进行复合,研究利用电气石的特性,提升过渡金属催化剂的活性、选择性、抗水抗硫性及其再生等各项性能。
现有低温脱硝催化剂中,文献[Low temperature selective catalyticreduction of NOx with NH3 over amorphous MnOx catalysts prepared by threemethods,X.Tang,et al.]报道了采用不同的水热制备条件合成具有不同微观形貌的MnOx催化剂的方法,实验虽然得出管状纳米MnOx催化剂低温脱硝效率最佳,但是其结果表明,单一氧化物的形貌改性实验并不足以将MnOx的催化活性达到工业低温脱硝的水平,尤其是单一MnOx催化剂的抗硫特性很差,需要引入其他过渡元素进行改性,这一缺点在CN106166493A中所制备的MnOx催化剂同样存在。文献[Low-temperature selectivecatalytic reduction of NO with NH3 over iron and manganese oxides supportedon titania,T.R.Yang,et al.]中报道了采用共沉淀法以Fe元素作为掺杂元素对Mn-TiO2低温SCR催化剂进行了改性,虽然实验结论得出Fe-Mn电荷转移能够提升MnOx的催化效率,但是共沉淀发制备出的Fe-Mn氧化物明显存在团聚现象,并且锐钛矿TiO2的生成过程和Mn2+的氧化过程存在冲突,当锐钛矿TiO2生成时,催化剂中依然存在大量Mn2+。本课题组先前研究的脱硝催化剂中,CN106111146A中阐述了一种制备含电气石的铁基脱硝催化剂的方法,其活性温度窗口为220~400℃,很明显不符合水泥窑所需脱硝催化剂的要求,同样的问题出现在CN106111123A中制得的含电气石的负载型锰基复合氧化物脱硝催化剂上。CN106975513A中制得的负载型电气石稀土复合选择性脱硝催化剂低温催化活性较好,120℃时就能达到97.7的NO脱除率,但是所用的SBA-15分子筛的价格高昂,制备工艺复杂,限制了其大规模使用,CN107051572A所制得含电气石的锰基脱硝催化剂亦是如此,因此不适合作为水泥窑用脱硝催化剂。
综上所述,现有技术中尚没有一种能够大规模应用于水泥窑烟气脱硝的低温SCR脱硝催化剂。本发明选用Cu-SAPO-34做为铁锰铈复合催化剂载体,提升铁锰铈复合催化剂比表面积,使活性位点良好的分散在载体Cu-SAPO-34表面及孔道内,利于反应气体的吸附。并且向负载型铁锰复合氧化物催化剂中添加铁电气石,利用电气石的自发极化作用对液相中离子进行吸附,会对晶体的生长过程起到控制作用,从而避免活分组分烧结团聚,使活性组分在载体上分散良好。
发明内容
本发明的目的为针对当前技术中存在的不足,提供一种含电气石的Mn,Fe,Ce/Cu-SAPO-34脱硝催化剂及其制备方法,利用离子交换法将铜离子嵌入含模板剂的分子筛骨架中,再用分子设计分散法将铁、锰、铈以及电气石颗粒均匀附着在分子筛表面,最后通过一次焙烧同时完成除去模板剂和催化剂活化处理。制得的新型催化剂以Ce/Cu-SAPO-34为基体,铁、锰离子在沉积过程中受电气石的自发极化作用影响,以电气石颗粒为中心生长为蜂窝状的多孔膜结构。以较低的成本制得效果更优的新型低温SCR脱硝催化剂,克服了现有技术中低温SCR脱硝催化剂低温活性不好、工艺复杂、制备成本高和抗硫和抗水能力较低等缺点。
本发明采取的技术方案为:
一种用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂,该催化剂包括载体、助剂和活性组分;所述的载体为Cu-SAPO-34分子筛,助剂为铈元素和电气石,活性组分为锰盐和铁盐;
其中,SAPO-34分子筛来源于含模板剂的分子筛合成浆料;锰元素负载量为5~20%wt,铁元素负载量为1~10%wt,铈元素负载量为0.1%~1.0%wt;铜元素的负载量为1.0~3.0%wt,电气石的负载量为0.1%~3%wt;制得催化剂晶体尺寸为1.0~3.5μm,比表面积为450~600㎡/g。
所述的催化剂经离子交换法和分子设计分散法制备而成;
所述的铜盐为硝酸铜、硫酸铜的一种或几种,所述的锰盐为乙酰丙酮锰(II),所述的铁盐为硝酸铁、乙酸铁、硫酸铁的一种或几种,所述的铈盐为硝酸铈;
所述的电气石为经氢氟酸水热处理的铁电气石,平均粒径为40~60nm。
所述的用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂的制备方法,包括以下步骤:
1)将SAPO-34粉末加入到含有铜盐和铈盐的混合溶液中,再加入稀硝酸调节溶液pH值=3~5,在60~80℃下反应1.5~3h后,过滤,然后用去离子水洗涤截留的粉体至中性,然后干燥;
其中,混合溶液中铜盐浓度为0.1~2mol/L,铈盐浓度为0.01~0.1mol/L;质量比SAPO-34粉末:混合溶液=1:50~80;所述的稀硝酸的浓度为0.5~2mol/L;
2)根据负载量,称取(1)步骤得到的干燥的粉体、以及相对应质量的锰盐和铁盐,加入到丙酮中,在室温下搅拌0.5~2h,再加入相应质量的电气石,继续搅拌0.1~1h;
其中,质量比(锰盐+铁盐):丙酮=1:30~70;
3)将溶液置于超声反应器中进行超声处理1~2h,所得溶液继续在室温下搅拌直到溶剂挥发形成暗黄色干胶状固体;
4)将所得干胶状固体在80~120℃干燥6~12h后获得的粉末置于管式炉中焙烧,在空气气氛下以0.5~2℃·min-1升至300~500℃焙烧5~10h,冷却到室温后制得催化剂。
本发明的实质性特点为:
本发明为电气石和Mn,Fe,Ce负载于Cu-SAPO-34分子筛的新组成;组成方面,此前从未有人将电气石和Mn,Fe,Ce同时负载于Cu-SAPO-34的载体之上,本发明利用几种元素和分子筛本身的催化性能优势互为补充,并利用电气石的微电场促进金属离子在溶液中的运动,以改善活性成分的团聚现象,从而制备出性能优异的脱硝催化剂。制备方法中关键步骤是:1、用离子交换法将铜离子嵌入含模板剂的分子筛骨架;2、通过一次焙烧同时完成除去模板剂和催化剂活化处理。关键物料是乙酰丙酮锰(II),这种锰的有机盐在丙酮中以分子形式存在,附着在分子筛上时更加均匀,不易团聚。
本发明的有益效果为:
1)本发明采用天然矿石铁电气石为活性助剂,有助于降低催化剂成本,制备工艺简单。
2)本发明将分子筛去除模板剂的过程与催化剂焙烧过程合二为一,大大节约了催化剂生产所需能源,达到了节能环保的目的。
3)本发明采用离子交换法和分子设计分散法,保证了活性组分在载体上的均匀分布,确保了各组分的优势互补,改善单一组分催化剂的性能。
4)脱硝催化剂在80℃时具有88.6%的NO转化率,在110~320℃区间内具有96%的NO转化率,与无负载不含电气石的脱硝催化剂相比,在80℃时NO脱除率提升30%。
5)并且在170℃时,通入SO2和H2O后,所制备的脱硝催化剂的NO转化率仍能保持在75%以上,所以具有较高的抗SO2和H2O中毒性能。
附图说明
图1为实施例1~6的NOx转化率效果图,
图2为170℃时实施例5的NOx转化率效果图
具体实施方式
以下通过特定的具体实例说明本发明的实施方法,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方法加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。
所述的载体SAPO-34分子筛为市售公知材料,由分子筛半成品在催化剂制备过程中加工而成,购买自南开大学催化剂厂。
本发明所述的铈元素、铜元素、电气石的负载量是以添加的铈元素、铜元素、电气石的质量与所用载体的质量的百分比得出的。活性组分指的是铜元素、锰元素和铁元素,锰元素与铁元素的负载量是分别以硝酸锰和硝酸铁混合溶液中的锰元素的质量、铁元素的质量和所用载体的质量的比值得出的。
所述的电气石为经0.1mol/L氢氟酸经180℃水热处理4h的铁电气石,平均粒径为50nm。所用的铁电气石产自河南西峡公司。
实施例1
按固液质量比为1:50的比例,将3g的SAPO-34粉末加入到不断搅拌的含有0.1mol/L硝酸铜(Cu(NO3)2)和0.04mol/L硝酸铈(Ce(NO3)3·6H2O)溶液中,再加入1mol/L稀硝酸调节溶液pH=5.2,在80℃下进行离子交换;待2h后反应完成,过滤交换液,并用去离子水洗涤截留的粉体至滤液pH值=7.0;将上述粉体干燥,然后与乙酰丙酮锰(II)(C10H14MnO4)1.38g和硝酸铁(Fe(NO3)3·9H2O)2.16g溶于106.2g丙酮中得到混合溶液,使Mn元素的负载量为10%,Fe元素的负载量为10%,在室温下磁力搅拌使溶液混合均匀;将溶液置于超声反应器中进行超声处理1h(温度30℃,功率400W),所得溶液继续在室温下搅拌直到形成暗黄色干胶状固体,取出在烘箱中100℃干燥8h;然后置于马弗炉中以1℃/min的升温速率升至400℃温度条件下煅烧5h,同时完成除去模板剂和催化剂活化处理,随炉冷却至室温取出磨碎后筛分,取粒度为40~60目备用,制备得到催化剂A。通过ICP测定出催化剂中Cu元素的负载量为1.2%,Ce元素的负载量为0.3%。本组催化剂未添加电气石,SEM结果显示催化剂晶体尺寸为1.5~2.8μm,BET结果显示催化剂比表面积为520.655㎡/g。
实施例2
按固液质量比为1:50的比例,将3g的SAPO-34粉末加入到不断搅拌的含有0.1mol/L硝酸铜(Cu(NO3)2)和0.04mol/L硝酸铈(Ce(NO3)3·6H2O)溶液中,再加入1mol/L稀硝酸调节溶液pH=5.2,在80℃下进行离子交换;待2h后反应完成过滤交换液,并用去离子水洗涤截留的粉体至滤液pH值=7.0;将上述粉体干燥后与乙酰丙酮锰(II)(C10H14MnO4)1.38g和硝酸铁(Fe(NO3)3·9H2O)2.16g溶于106.2g丙酮中得到混合溶液,使Mn元素的负载量为10%,Fe元素的负载量为10%,在室温下磁力搅拌使溶液混合均匀;加入电气石粉末0.03g,使电气石的负载量为1%,继续搅拌1h,将溶液置于超声反应器中进行超声处理1h(温度30℃,功率400W),所得溶液继续在室温下搅拌直到形成暗黄色干胶状固体,取出在烘箱中100℃干燥8h;然后置于马弗炉中以1℃/min的升温速率升至400℃温度条件下煅烧5h,同时完成除去模板剂和催化剂活化处理,随炉冷却至室温取出磨碎后筛分,取粒度为40~60目备用,制备得到催化剂A。通过ICP测定出催化剂中Cu元素的负载量为1.2%,Ce元素的负载量为0.3%。SEM结果显示催化剂晶体尺寸为1.7~3.1μm,BET结果显示催化剂比表面积为546.286㎡/g。
实施例3
按固液质量比为1:50的比例,将3g的SAPO-34粉末加入到不断搅拌的含有0.1mol/L硝酸铜(Cu(NO3)2)和0.04mol/L硝酸铈(Ce(NO3)3·6H2O)溶液中,再加入1mol/L稀硝酸调节溶液pH=5.2,在80℃下进行离子交换;待2h后反应完成过滤交换液,并用去离子水洗涤截留的粉体至滤液pH值=7.0;将上述粉体干燥后与乙酰丙酮锰(II)(C10H14MnO4)1.38g和硝酸铁(Fe(NO3)3·9H2O)2.16g溶于106.2g丙酮中得到混合溶液,使Mn元素的负载量为10%,Fe元素的负载量为10%,在室温下磁力搅拌使溶液混合均匀;加入电气石粉末0.06g,使电气石的负载量为2%,继续搅拌1h,将溶液置于超声反应器中进行超声处理1h(温度30℃,功率400W),所得溶液继续在室温下搅拌直到形成暗黄色干胶状固体,取出在烘箱中100℃干燥8h;然后置于马弗炉中以1℃/min的升温速率升至400℃温度条件下煅烧5h,同时完成除去模板剂和催化剂活化处理,随炉冷却至室温取出磨碎后筛分,取粒度为40~60目备用,制备得到催化剂A。通过ICP测定出催化剂中Cu元素的负载量为1.2%,Ce元素的负载量为0.3%。SEM结果显示催化剂晶体尺寸为1.4~3.0μm,BET结果显示催化剂比表面积为547.777㎡/g。
实施例4
步骤如实施例3,其他条件不变,改变电气石质量为0.09g,使电气石的负载量为3%,制得催化剂D。SEM结果显示催化剂晶体尺寸为1.5~3.0μm,BET结果显示催化剂比表面积为486.257㎡/g。
实施例5
步骤如实施例3,其他条件不变,改变乙酰丙酮锰(II)(C10H14MnO4)质量为2.76g,Mn元素的负载量为20%,制得催化剂E。SEM结果显示催化剂晶体尺寸为1.4~3.0μm,BET结果显示催化剂比表面积为498.540㎡/g。
实施例6
步骤如实例3所示,其他条件变不变,改变(Fe(NO3)3·9H2O)质量为3.25g,使得Fe元素的负载量为15%。制得催化剂F。SEM结果显示催化剂晶体尺寸为1.6~3.2μm,BET结果显示催化剂比表面积为494.992㎡/g。
催化活性测试
将实施例制得的含电气石的铁基复合氧化物催化剂A、B、C、D、E和F应用于NH3-SCR反应,具体反应条件如下:催化反应性能数据是在固定床连续流动石英反应器中进行测定。催化剂粒度为40~60目,用量为2mL,反应气体组成为:500ppm NO、500ppm NH3、5%(体积百分比)O2,N2作为平衡气,气体总流量为1000mL/min,气体空速比为30000h-1。在反应前,催化剂需用高纯N2在300℃下预处理1h,催化反应在50~320℃下进行,每升高30℃采集一次数据,每次在反应达到平衡后用KM940型烟气分析仪采集催化性能数据。催化剂的脱硝效率采用如下公式计算:
反应结果如表1和图1所示。
在相同实验条件下,通过对催化剂A、B、C、D、E、F的活性测试结果比较可知,催化剂A不含电气石,在200℃时达到76.8%的NO脱除率。与A催化剂相比,催化剂B、C和D在较低温度下(110℃)时就具有更高的NO转化率以及更宽泛的活性温度窗口,所以可以看出,铁电气石的添加不仅可以提升催化剂的低温活性,并且可以拓宽其活性温度窗口。并且当电气石的负载量为2%时,催化剂C活性最高,在110℃具有82.3%的NO转化率。改变Mn元素的负载量为20%后制备出催化剂E和改变Fe元素的负载量为15%后制备出催化剂F。研究发现,催化剂E(即Mn元素的负载量为20%,铁元素的负载量为10%,电气石负载量为2%时)具有最高的NO脱除率,在110~320℃区间内具有95%以上的NO脱除率。
表1不同含电气石的负载型铁锰低温脱硝催化剂氮氧化物脱除率
实施例7
取实施例5中的催化剂E 2mL为实验对象,在170℃时,N2作为平衡气,气体总流量为1000mL/min,气体空速比为30000h-1,气体组成为500ppm NO、500ppm NH3、5%(体积百分比)O2下,反应10分钟后,向体系中通入200ppm的SO2,并每隔30min用KM940型烟气分析仪采集一次数据并记录。结果如表2及图2所示,催化剂的NO脱除率由97.8%降至84%左右。当通入SO2 300min后停止通入,NO脱除率慢慢恢复至90%左右。
图2表示170℃时单独通入SO2或H2O以及共同通入SO2和H2O后,催化剂的NO脱除率仍能保持在84%、79%、74%左右,证明催化剂具有较高的抗SO2和H2O中毒性能。
实施例8
取实施例5中的催化剂2mL为实验对象,在170℃时,N2作为平衡气,气体总流量为1000mL/min,气体空速比为30000h-1,气体组成为500ppm NO、500ppm NH3、5%(体积百分比)O2下,反应10分钟后,向体系中通入10%的水蒸汽后,并每隔30min用KM940型烟气分析仪采集一次数据并记录。结果如表2及图2所示,催化剂的NO脱除率由97.8%降至79%左右,当通入水蒸气300min后停止通入,NO转化率慢慢恢复至85%左右。
实施例9
取实施例5中的催化剂2mL为实验对象,在170℃时,N2作为平衡气,气体总流量为1000mL/min,气体空速比为30000h-1,气体组成为500ppm NO、500ppm NH3、5%(体积百分比)O2下,反应10分钟后,向反应体系中通入10%H2O+200ppmSO2,并每隔30min用KM940型烟气分析仪采集一次数据并记录。结果如表2及图2所示,催化剂NO脱除率由97.8%降至75%左右,当通入10%H2O+200ppmSO2 300min后停止通入,催化剂NO脱除率慢慢恢复至82%左右。
综上所述,与现有的相同成本下制作的脱硝催化剂相比,本发明中的含电气石的铁锰低温脱硝催化剂不仅具有较高的低温SCR活性,并且具有优良的抗SO2和H2O的中毒性能。具有广阔的应用前景。
表2为170℃时不同实验条件下催化剂E的NOx脱除率
本发明未尽事宜为公知技术。
Claims (5)
1.一种用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂,其特征为该催化剂包括载体、助剂和活性组分;所述的载体为Cu-SAPO-34分子筛,助剂为铈元素和电气石,活性组分为锰盐和铁盐;
其中,锰元素负载量为5~20% wt ,铁元素负载量为1~10% wt,铈元素负载量为0.1%~1.0% wt;铜元素的负载量为1.0~3.0% wt,电气石的负载量为0.1%~3% wt。
2.如权利要求1所述的用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂,其特征为所述的催化剂晶体尺寸为1.0~3.5μm,比表面积为450~600㎡/g。
3.如权利要求1所述的用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂的制备方法,其特征为包括以下步骤:
1)将SAPO-34粉末加入到含有铜盐和铈盐的混合溶液中,再加入稀硝酸调节溶液Ph值=3~5,在60~80℃下反应1.5~3h后,过滤,然后用去离子水洗涤截留的粉体至中性,然后干燥;
其中,混合溶液中铜盐浓度为 0.1~2mol/L,铈盐浓度为0.01~0.1 mol/L;质量比SAPO-34粉末:混合溶液=1:50~80;所述的稀硝酸的浓度为0.5~2mol/L;
2)根据负载量,将得到的干燥的粉体、锰盐和铁盐,加入到丙酮中,在室温下搅拌0.5~2h,再加入电气石,继续搅拌0.1~1h;
其中,质量比(锰盐+铁盐):丙酮=1:30~70;
3)将溶液置于超声反应器中进行超声处理1~2h,所得溶液继续在室温下搅拌直到溶剂挥发形成暗黄色干胶状固体;
4)将所得干胶状固体在80~120℃干燥6~12h后获得的粉末置于管式炉中焙烧,在空气气氛下以0.5~2℃•min-1升至300~500℃焙烧5~10h,冷却到室温后制得催化剂。
4.如权利要求3所述的用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂的制备方法,其特征为所述的铜盐为硝酸铜、硫酸铜的一种或几种,所述的锰盐为乙酰丙酮锰(II),所述的铁盐为硝酸铁、乙酸铁、硫酸铁的一种或几种,所述的铈盐为硝酸铈。
5.如权利要求3所述的用于水泥窑含电气石的Mn,Fe,Ce/Cu-SAPO-34低温脱硝催化剂的制备方法,其特征为所述的电气石为经氢氟酸水热处理的铁电气石,平均粒径为40~60nm。
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