CN111921555B - 一种no分解脱硝的催化剂及其制备方法和应用 - Google Patents
一种no分解脱硝的催化剂及其制备方法和应用 Download PDFInfo
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- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 50
- 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 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 6
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- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
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- 239000011651 chromium Substances 0.000 abstract description 2
- 229910052741 iridium Inorganic materials 0.000 abstract description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract 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 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052703 rhodium Inorganic materials 0.000 abstract description 2
- 239000010948 rhodium Substances 0.000 abstract description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 113
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
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- 239000002131 composite material Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 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 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000012691 Cu precursor Substances 0.000 description 1
- 241001147101 Dugong Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Abstract
本发明涉及一种NO分解脱硝的催化剂及其制备方法和应用,属于废气脱硝技术领域。本发明所述催化剂包括活性组分、分子筛;所述活性组分为铁、钴、镍、锰、铂、铑、钯、钌、铱、铬和银中的至少一种;所述分子筛为ZSM‑5、ZSM‑11、ZSM‑12、ZSM‑35、SSZ‑13、SSZ‑23、SAPO‑34、SAPO‑35、AIPO‑33和Beta中的至少一种;所述活性组分占催化剂重量百分比的0.02‑10.00wt.%。本发明所述催化剂可为我国在IMO限硝令下船舶正常营运提供了保障,打破欧美对高端船配产品的垄断,促进我国向造船强国发展。
Description
技术领域
本发明涉及一种NO分解脱硝的催化剂及其制备方法和应用,属于废气脱硝技术领域。
背景技术
氮氧化物(NOx)是严重危害人类健康的主要大气污染物之一,主要来源于固定源(发电厂、工业锅炉等)和移动源(船舶、机动车等)。其中,固定源采用的氨选择性催化还原(NH3-SCR)脱硝技术已成熟并得到了成功的应用。值得注意的是,海洋运输承担了贸易运输总量的90%,其快速发展引起船舶废气NOx排放急剧增加,污染严重且严峻。为此,国际海事组织(IMO)规定从2016年1月1日起实施船舶废气中NOx排放需达到IMO TierⅢ标准。强制履行IMO公约已不可逆转,因此试验筛选优势脱硝技术用于移动源船舶脱硝已迫在眉睫。
然而,固定源所采用的NH3-SCR脱硝技术是以氨气为还原剂,氨气消耗量大、运输和存储存在安全隐患且氨气易产生二次污染,所用设备庞大、投资和运行费用高。结合船舶废气实际工况以及船舶使用空间限制,现有的NH3-SCR技术不适用于船舶等移动源所使用的柴油机尾气脱硝。
船舶废气NOx中90-95%为NO,对比现有脱硝技术并结合船舶实际工况,直接催化分解NO为N2和O2具有不使用还原剂、设备体积小、工艺简单、经济性好、且不产生二次污染等突出优点,是船舶废气最理想的脱硝途径。NO分解反应在热力学上可行(2NO→N2+O2,△rGm=-86.6KJ/mol),但反应活化能高达364KJ/mol导致反应受动力学限制,因此研发高效NO分解催化剂是该脱硝技术的核心。迄今,已报道的NO分解催化剂主要有贵金属、金属氧化物、钙钛矿型复合氧化物和分子筛。其中,前三类催化剂因NO分解产生的O2极易吸附在催化剂表面而产生“氧阻抑”,阻碍NO进一步分解,因此导致NO分解反应通常需要在800-900℃高温条件下催化剂才具有较高活性,而船舶排放的尾气温度通常低于400℃,因此贵金属、金属氧化物、钙钛矿型复合氧化物催化剂不适用于船舶废气脱硝。相比之下,分子筛催化剂通常在400-500℃低温条件下具有较高的NO分解活性。
目前,未见公开专利报道使用分子筛催化剂直接催化NO分解脱硝。但是,以下公开文献涉及到利用分子筛催化剂催化分解NO为N2和O2。自1986年Iwamoto等首次发现Cu-ZSM-5分子筛具有分解NO活性以来,后续研究主要围绕Cu-ZSM-5分子筛催化剂而展开,研究重点是Cu-ZSM-5分子筛催化剂的制备(Mater.Sci.-Poland,2016,34,177-184),铜前驱体(J.Chem.Technol.Biotechnol,2019,94,3356-3366),助剂改性(Catal.Today,2019,327,203-209;Appl.Catal.,A:General,2013,464-465,61-67;Adv.Mater.Res.,2010,113-116,1735-1739;Catal.Today,2007,126,284-289),分子筛种类及性质(Chem.Rev..2016,116,3658-3721;Catal.Commun.,2006,7,705-708;Appl.Catal.,B:Environ.,2006,67,60-67)。
然而,Cu-ZSM-5分子筛虽然低温活性好,但其具有抗SO2和O2中毒能力差的致命缺陷。一方面,SO2分子和O2分子与NO在Cu-ZSM-5分子筛催化剂活性位上发生竞争吸附,抑制NO吸附,进而降低NO脱除率。另一方面,SO2易于Cu-ZSM-5分子筛催化剂的铜物种发生化学反应生成硫酸铜盐,导致Cu-ZSM-5分子筛催化剂完全中毒失去分解NO活性。迄今,未有公开专利和文献报道在SO2气氛中来优选NO分解脱硝分子筛催化剂。
发明内容
本发明通过制备新的催化剂,解决了上述的问题。
本发明提供了一种NO分解脱硝的催化剂,所述催化剂包括活性组分、分子筛;所述活性组分为铁、钴、镍、锰、铂、铑、钯、钌、铱、铬和银中的至少一种;所述分子筛为ZSM-5、ZSM-11、ZSM-12、ZSM-35、SSZ-13、SSZ-23、SAPO-34、SAPO-35、AIPO-33和Beta中的至少一种;所述活性组分占催化剂重量百分比的0.02-10.00wt.%。
本发明优选为所述活性组分为铁、钴和镍中的至少一种。
本发明优选为所述活性组分为铁、钴、镍或铁镍。
本发明优选为所述分子筛为ZSM-5、ZSM-11、SSZ-13、SAPO-34或Beta。
本发明另一目的为提供一种上述催化剂的制备方法,所述制备方法为:将焙烧后分子筛与含有活性组分的硝酸盐溶液混合,在50-80℃下搅拌1-3h,分离,再将分离所得固体洗至中性,干燥,然后在等离子体气氛中400-550℃焙烧0.5-3h。
本发明优选为所述等离子体气氛为空气、N2、Ar、He和H2中的至少一种。
本发明又一目的为提供一种上述催化剂在高浓度SO2和O2下脱硝的应用。
本发明优选为所述应用方法为:SO2的浓度为300-800ppm,O2的浓度为5-15vol%,NO的浓度为500-1500ppm,反应温度为200-450℃。
本发明有益效果为:
本发明所述的催化剂可以将NO直接分解为N2和O2,具有不产生二次污染、不使用还原剂、经济性好、工艺简单等突出优点,是最理想的脱硝途径,尤其适用于船舶等移动源所使用的柴油机尾气脱硝。
本发明所述的催化剂实现了在SO2浓度500ppm、O2浓度10vol.%和NO浓度1000ppm的复杂气氛中及350℃低温条件下,NO脱除率高达45.5%;此外,本发明所述的催化剂也具有脱除SO2能力,SO2脱除率为30%。
本发明所述的催化剂可为我国在IMO限硝令下船舶正常营运提供了保障,打破欧美对高端船配产品的垄断,促进我国向造船强国发展。
附图说明
本发明附图1幅,
图1为对比例1-2、实施例1-3的NO脱除率。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
下述对比例和实施例所用的原料气是模拟船舶尾气气氛,原料气为NO浓度1000-1200ppm、SO2浓度450-500ppm、O2浓度10vol%,N2为平衡气,原料气总流量1.0-1.1L/min;所用的NO分解反应器为连续流动式固定床石英反应器;催化剂填充于石英反应器的反应区,催化剂填充量2g,对应的反应区长度50-65mm、空速15000-20000h-1;反应温度300-550℃;使用马杜红外烟气分析仪检测并评价不同催化剂的NO分解脱硝效果。
对比例1
在NO分解反应器中未填充催化剂,研究反应温度对脱硝性能的影响,结果见表1和图1。
结论:在不同反应温度下,NO浓度变化不明显,说明在没有催化剂参与的条件下,单纯提高反应温度并不能达到脱除NO的目的。
对比例2
一种Cu-ZSM-5催化剂的制备方法,所述制备方法为:将焙烧后ZSM-5分子筛与硝酸铜溶液混合,在70℃下搅拌2h,分离,再将分离所得固体洗至中性,120℃干燥3h,然后在空气等离子体气氛中500℃焙烧3h,得到铜占催化剂重量百分比0.51wt.%的Cu-ZSM-5催化剂。
在NO分解反应器中填充Cu-ZSM-5催化剂,结果见表1和图1。
实施例1
一种Ni-ZSM-5催化剂的制备方法,与实施例1的区别为:将焙烧后ZSM-5分子筛与硝酸镍溶液混合,得到镍占催化剂重量百分比0.43wt.%的Ni-ZSM-5催化剂。
在NO分解反应器中填充Ni-ZSM-5催化剂,结果见表1和图1。
实施例2
一种Co-ZSM-5催化剂的制备方法,与实施例1的区别为:将焙烧后ZSM-5分子筛与硝酸钴溶液混合,得到钴占催化剂重量百分比0.41wt.%的Co-ZSM-5催化剂。
在NO分解反应器中填充Co-ZSM-5催化剂,结果见表1和图1。
实施例3
一种Fe-ZSM-5催化剂的制备方法,与实施例1的区别为:将焙烧后ZSM-5分子筛与硝酸铁溶液混合,得到铁占催化剂重量百分比0.33wt.%的Fe-ZSM-5催化剂。
在NO分解反应器中填充Fe-ZSM-5催化剂,结果见表1和图1。
实施例4
一种Fe-Ni-ZSM-5催化剂的制备方法,所述制备方法为:1)将焙烧后ZSM-5分子筛与硝酸镍溶液混合,在70℃下搅拌2h,分离,再将分离所得固体洗至中性,120℃干燥3h,然后在空气等离子体气氛中500℃焙烧3h,得到Ni-ZSM-5催化剂;2)将Ni-ZSM-5催化剂与硝酸铁溶液混合,在70℃下搅拌2h,分离,再将分离所得固体洗至中性,120℃干燥3h,然后在空气等离子体气氛中500℃焙烧3h,得到铁和镍占催化剂重量百分比0.82wt.%的Fe-Ni-ZSM-5催化剂。
在NO分解反应器中填充Fe-Ni-ZSM-5催化剂,结果见表1。
结论:与对比例1相比,填充分子筛催化剂显著提高了NO脱除率,并且不同金属与ZSM-5的协同作用对NO脱硝效果影响很大;此外,分子筛催化剂也显著促进了SO2脱除。在高浓度SO2和高浓度O2的复杂气氛下,活性组分Fe具有最高NO脱除能力,其次是Co和Ni,而Cu对应的NO脱除能力最差。值得注意的是,迄今报道的用于NO分解脱硝的分子筛催化剂研究中,采用的模拟反应原料气主要由NO/N2或NO/O2/N2组成,不含SO2,研究指出在脱硝过程中引入浓度低于100ppm的SO2就会导致分子筛催化剂脱硝性能快速降低。显然,模拟真实废气气氛对研发优选NO分解脱硝催化剂及脱硝技术实际应用至关重要。
实施例5
一种Fe-SSZ-13催化剂的制备方法,与实施例4的区别为:将焙烧后SSZ-13分子筛与硝酸铁溶液混合,得到铁占催化剂重量百分比0.31wt.%的Fe-SSZ-13催化剂。
在NO分解反应器中填充Fe-SSZ-13催化剂,结果见表1。
实施例6
一种Fe-SAPO-34催化剂的制备方法,与实施例4的区别为:将焙烧后SAPO-34分子筛与硝酸铁溶液混合,得到铁占催化剂重量百分比0.33wt.%的Fe-SAPO-34催化剂。
在NO分解反应器中填充Fe-SAPO-34催化剂,结果见表1。
实施例7
一种Fe-ZSM-11催化剂的制备方法,与实施例4的区别为:将焙烧后ZSM-11分子筛与硝酸铁溶液混合,得到铁占催化剂重量百分比0.35wt.%的Fe-ZSM-11催化剂。
在NO分解反应器中填充Fe-ZSM-11催化剂,结果见表1。
实施例8
一种Fe-Beta催化剂的制备方法,与实施例4的区别为:将焙烧后Beta分子筛与硝酸铁溶液混合,得到铁占催化剂重量百分比0.42wt.%的Fe-Beta催化剂。
在NO分解反应器中填充Fe-Beta催化剂,结果见表1。
结论:在高浓度SO2和高浓度O2的复杂气氛下,分子筛催化剂的分子筛种类对其脱硝性能有一定的影响,主要体现在分子筛的酸性质和孔尺寸影响分子筛催化剂脱硝性能。其中,分子筛酸性质直接影响分子筛催化剂的金属交换量,进而影响分子筛催化剂的NO分解性能;而分子筛孔尺寸直接影响SO2在分子筛催化剂金属活性位的吸附性能,SAPO-34分子筛和SSZ-13分子筛的孔尺寸小于抑制SO2(分子尺寸/>)进入分子筛孔道内,阻止SO2在分子筛孔道内金属活性位上吸附,进而提高催化剂的耐硫性。
表1
NO转化率(%) | 最佳脱硝温度(℃) | |
对比例1 | 0.2 | 400 |
对比例2 | 14.1 | 350 |
实施例1 | 23.9 | 400 |
实施例2 | 31.0 | 350 |
实施例3 | 36.6 | 400 |
实施例4 | 40.2 | 400 |
实施例5 | 45.5 | 350 |
实施例6 | 41.3 | 400 |
实施例7 | 42.7 | 350 |
实施例8 | 24.2 | 400 |
Claims (5)
1.一种NO分解脱硝的催化剂在高浓度SO2和O2下NO分解脱硝的应用,其特征在于:所述催化剂包括活性组分、分子筛;
所述活性组分为铁、钴、镍中的至少一种;
所述分子筛为ZSM-5、ZSM-11、ZSM-12、ZSM-35、SSZ-13、SSZ-23、SAPO-34、SAPO-35、AIPO-33和Beta中的至少一种;
所述活性组分占催化剂重量百分比的0.02-10.00wt.%;
所述SO2的浓度为300-800ppm,O2的浓度为5-15vol%,NO的浓度为500-1500ppm,反应温度为200-450℃。
2.根据权利要求1所述NO分解脱硝的催化剂在高浓度SO2和O2下NO分解脱硝的应用,其特征在于:所述活性组分为铁、钴、镍或铁镍。
3.根据权利要求1所述NO分解脱硝的催化剂在高浓度SO2和O2下NO分解脱硝的应用,其特征在于:所述分子筛为ZSM-5、ZSM-11、SSZ-13、SAPO-34或Beta。
4.根据权利要求1、2或3所述NO分解脱硝的催化剂在高浓度SO2和O2下NO分解脱硝的应用,其特征在于:所述催化剂的制备方法为:将焙烧后分子筛与含有活性组分的硝酸盐溶液混合,在50-80℃下搅拌1-3h,分离,再将分离所得固体洗至中性,干燥,然后在等离子体气氛中400-550℃焙烧0.5-3h。
5.根据权利要求4所述NO分解脱硝的催化剂在高浓度SO2和O2下NO分解脱硝的应用,其特征在于:所述等离子体气氛为空气、N2、Ar、He和H2中的至少一种。
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