CaO/ZrO_2固体碱催化水解CFC-12的研究
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摘要
采用沉淀过饱和浸渍法制备CaO/ZrO_2固体碱催化剂,通过XRD、 SEM、 EDS、 N_2吸附-脱附、 FT-IR和CO_2-TPD表征手段对催化剂进行表征,同时研究了催化剂焙烧温度、催化水解温度、水蒸气浓度与总流量对CFC-12转化率的影响.结果表明,在焙烧温度为500℃、催化水解温度为400℃、水蒸气浓度为25%、总流量为5 mL/min时CFC-12的转化率最高,达到95.80%,主要产物为HCl、 HF和CO_2,副产物为CFC-13.表征结果表明其为典型的介孔材料,并且纯度较高,经过焙烧后CaO和ZrO_2形成了固溶体, 500℃焙烧的催化剂具有较高的比表面积和孔容,焙烧温度过高催化剂会烧结成块,孔结构遭到破坏. CO_2-TPD表征结果表明催化剂的活性中心为碱,并且高的焙烧温度会降低其碱性.
CaO/ZrO_2 solid base catalyst was prepared by precipitation supersaturation impregnation method. The catalyst was characterized by XRD, SEM, EDS, N_2 adsorption-desorption, FT-IR and CO_2-TPD. The effects of calcination temperature, hydrolysis temperature, water vapor concentration and total flow rate on CFC-12 conversion were studied. The results showed that the CFC-12 conversion could reach 98.50% by using CaO/ZrO_2 solid base as the catalyst at calcination temperature of 500 ℃, a hydrolysis temperature of 400 ℃, a water vapor concentration of 25% and a total flow rate of 5 mL/min and the main hydrolysis products were HCl, HF and CO_2 and the by-product was CFC-13. The characterization results showed that CaO/ZrO_2 solid base catalyst was a typical mesoporous with high purity. After calcination, CaO and ZrO_2 formed a solid solution. The calcined catalyst at 500 ℃ had a high specific surface area and pore volume. If the calcination temperature was too high, the catalyst would be sintered into a block and the pore structure was destroyed. CO_2-TPD characterization results indicated that the active center of the catalyst was base and a high calcination temperature lowered its basicity.
CaO/ZrO_2 solid base catalyst was prepared by precipitation supersaturation impregnation method. The catalyst was characterized by XRD, SEM, EDS, N_2 adsorption-desorption, FT-IR and CO_2-TPD. The effects of calcination temperature, hydrolysis temperature, water vapor concentration and total flow rate on CFC-12 conversion were studied. The results showed that the CFC-12 conversion could reach 98.50% by using CaO/ZrO_2 solid base as the catalyst at calcination temperature of 500 ℃, a hydrolysis temperature of 400 ℃, a water vapor concentration of 25% and a total flow rate of 5 mL/min and the main hydrolysis products were HCl, HF and CO_2 and the by-product was CFC-13. The characterization results showed that CaO/ZrO_2 solid base catalyst was a typical mesoporous with high purity. After calcination, CaO and ZrO_2 formed a solid solution. The calcined catalyst at 500 ℃ had a high specific surface area and pore volume. If the calcination temperature was too high, the catalyst would be sintered into a block and the pore structure was destroyed. CO_2-TPD characterization results indicated that the active center of the catalyst was base and a high calcination temperature lowered its basicity.
引文
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[3] Doxon R.Global environmental facility investments in the phase-out of ozone-depleting substances [J].Mitig Adapt Strat Glob Change,2011,16(5):567-584.
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[5] Dameris M.Climate change and atmospheric chemistry:How will the stratospheric ozone layer develop [J].Angew Chem Int Ed,2010,49(44):8092-8102.
[6] Miao Pei-bi(缪培碧).Destroy of Freon in a cement kiln(在水泥窑中销毁氟利昂)[J].Fore Buil Mat Trans(国外建材译丛),1997,9(1) :49-52.
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[9] Wu Jian-ping(吴建平).Decomposition of Freon by plasma method(用等离子法分解氟利昂)[J].Cry Spec Gases(低温与特气),1990,1990(3) :53-54.
[10] Zakharenko V S,Parmon V N.Photoadsorption and photocatalytic processes affecting the composition of the Earth’s atmosphere:II.Dark and photostimulated adsorption of Freon 22 (CHF2Cl) on MgO[J].Kinet Catal,2000,41(6):756-759.
[11] Mel’nikov M Y,Baskakov D V,Feldman V I.Spectral characteristics and transformations of intermediates in irradiated Freon 11,Freon 113,and Freon 113a[J].High Energy Chem,2002,36(5):309-315
[12] Hirai K,Nagata Y,Maeda Y.Decomposition of chlorofluorocarbons and hydrofluorocarbons in water by ultrasonic irradiation[J].Ultrason Sonochem,1996,3(3):S205-S207.
[13] Pinnock S,Hurley M D,Shine K P,et al.Radiative forcing of climate by hydrochlorofluorocarbons and hydrofluorocarbons[J].J Geophys Res Atmos,1995,100(D11):23227-23238.
[14] Zhang Jian-jun(张建君),Xu Mao-qian(许茂乾).Studies on catalytic hydrogenation of CFC-12(CFC-12的催化加氢研究) [J].J Ningxia Univer:Nat Sci Edit(宁夏大学学报(自然科学版) ),2001,22(2):211-212.
[15] Nagata H,Takakura T,Tashiro S,et al.Catalytic oxidative decomposition of chlorofluorocarbons (CFCs) in the presence of hydrocarbons[J].Appl Catal B:Environ,1994,5(1/2):23-31.
[16] Lin Yong-da(林永达),Chen Qing-yun(陈庆云).Atmospheric ozone layer depletion and CFCs alternatives (大气臭氧层破坏和CFCs替代物)[J].Prog Chem(化学进展),1998,10(2) :228-235.
[17] Hou Jian(侯健),Han Gong-yuan(韩功元),Zhang Zhen-man(张振满),et al.Atmospheric degradation of CFC-12 by dielectric barrier discharge(氟利昂-12的常压DBD降解)[J].J Fudan Univer:Nat Sci Edit(复旦学报(自然科学版)),1999,38(6):627-630
[18] Gao Hong(高红).Study on Freon-12 premixed combustion hydrolysis(昆明理工大学博士论文)[D].Kunming Univer Sci Techno(昆明理工大学),2011.
[19] Zou Jin-bao(邹金宝).Study on decomposition of CFC-12 by molten alkali (salt)(昆明理工大学博士论文)[D].Kunming Univ Sci Techno(昆明理工大学),2009.
[20] Zhao Guang-qin(赵光琴),Jia Li-juan(贾丽娟),Tang Guang-yang(唐光阳),et al.Catalytic hydrolysis of CHC1F2 and CC12F2 by ZrO2 /TiO2 solid acid catalyst(TiO2/ZrO2固体酸催化水解CHC1F2和CC12 F2的研究)[J].Environ Engineer(环境工程),2017,35(S1):138-140.
[21] Ma Zhen(马臻),Hua Wei-ming(华伟明),Tang Yi(唐颐),et al.A novel catalyst WO3/A12O3 for decomposition of CFC-12(用以分解氟利昂-12的新型催化剂WO3/A12O3)[J].Chin J Appl Chem(应用化学),2000,17(3):319-321.
[22] Ma Zhen,Hua Weiming,Tang Yi,et al.A novel CFC-12 hydrolysis catalyst:WO3/SnO2[J].Chin Chem Lett,2000,11(1):87-88.
[23] Ma Zhen,Hua Wei-ming,Tang Yi,et al.Catalytic decomposition of CFC-12 over heteropolyacids[J].Chin J Catal,2000,21(1):3-4.
[24] Ma Zhen,Hua Wei-ming,Tang Yi,et al.Catalytic decomposition of CFC-12 over on solid acids SO42-/MxOy(M=Zr,Ti,Sn,Fe,Al)[J].Chin J Chem,2000,18(3):341-345.
[25] Ma Zhen,Hua Wei-ming,Tang Yi,et al.Catalytic hydrolysis of CFC-12 over solid acid Ti(SO4)2[J].Chin Chem Lett,2000,11(4):311-314.
[26] Hua Wei-ming,Zhang Feng,Ma Zhen,et al.Catalytic hydrolysis of chlorofluorocarbon (CFC-12) over WO3/ZrO2[J].Catal Lett,2000,65(1):85-89.
[27] Hua Wei-ming,Zhang Feng,Ma Zhen,et al.WO3/ZrO2 strong acid as a catalyst for the decomposition of chlorofluorocarbon (CFC-12) [J].Chem Res Chin Univer,2000,16(2):185-187
[28] Zheng Shu-jun(郑淑君).Solid base catalysts and its application(固体碱催化剂及其应用)[J].Chem Propell Polym Mater(化学推进剂与高分子材料),2001,2001(4):18-21.
[29] Li Xiang-zhao(李向召),Jiang Qi(江琦).Progress in catalysts for solid base(固体碱催化剂研究进展)[J].Nat Gas Chem Indus(天然气化工),2005,30(1):42-48.
[30] Lu Xiao-yong(鲁晓勇),Bao De-yan(鲍德艳),Su Ming-hua(苏明华).Study on the application of magnetic solid base catalyst in the preparation of biodiesel from palm oil(磁性固体碱催化剂在棕榈油制备生物柴油中的应用研究)[J].Pet Process Petrochem (石油炼制与化工),2008,39(8):55-58.
[31] Liu Chang(刘畅),Yan Fang(颜芳),Luo Wen(罗文),et al.Nano-magnetic solid basic catalyst for producing biodiesel(纳米磁性固体碱催化剂用于合成生物柴油的研究)[J].Mod Chem Indus(现代化工),2009,29(S2):167-171.
[32] Wang Huan-huan(王欢欢),Pang Dan-dan(庞丹丹),Zheng Yao(郑尧),et al.Biodiesel production from animal fat gutter oil by MgO /ZrO2 solid base catalyst(MgO-ZrO2固体碱催化废弃动物油制备生物柴油)[J].Chin J Environ Engineer(环境工程学报),2016,10(3):1484-1491.
[33] Liu Tian-cheng(刘天成).Study on ZrO2-based solid acid-base catalytic hydrolysis of low concentration Freon(昆明理工大学博士论文)[D].Kunming Univ Sci Techno(昆明理工大学),2010.
[34] Liu T C,Ning P,Wang H B,et al.Catalytic hydrolysis of CCl2F2 over solid base CaO/ZrO2 [J].Adv Mater Res,2013,652/654:1533-1538.
[35] Liu T C,Ning P,Wang H B,et al.Catalytic decomposition of CCl2F2 over solid base Na2O/ZrO2 [J].Adv Mater Res,2013,634/638:494-499.
[36] Liu T C,Guo Y J,Tang G Y,et al.Adsorption thermodynamics study on CCl2F2 over solid base Na2O/ZrO2 [J].Appl Mech Mater,2014,457/458:112-115.
[37] Zou Jin-bao(邹金宝),Ning Ping(宁平),Gao Hong(高红),et al.Study on combustion hydrolyzing technology in treating CFCs(氟利昂的燃烧水解法处理研究)[J].J Kunming Univer Sci Technol:Sci Technol Edit(昆明理工大学学报(理工版)),2009,34(1):92-94.
[38] Taltita Y,Wakamatsu H,Tokumaru M,et al.Decomposition of chlorofluorocarbons over metal phosphate ca- talysts Part III.Reaction path of CC12F2 decomposition over AlPO4[J].Appl Catal A:General,2000,194/195:55-61.
[39] Hattori H.Solid base catalysts:generation of basic sites and application to organic synthesis[J].Appl Catal A:Gener,2001,222:247-259.
[2] Molina M J,Rowland F S.Stratospheric sink for chlorofluoromethanes:Chlorine atomc-atalysed destruction of ozone [J].Nature,1974,249(5460):810-812.
[3] Doxon R.Global environmental facility investments in the phase-out of ozone-depleting substances [J].Mitig Adapt Strat Glob Change,2011,16(5):567-584.
[4] Dameris M.Depletion of the ozone layer in the 21st century [J].Angew Chem Int Ed,2010,49(3):489-491.
[5] Dameris M.Climate change and atmospheric chemistry:How will the stratospheric ozone layer develop [J].Angew Chem Int Ed,2010,49(44):8092-8102.
[6] Miao Pei-bi(缪培碧).Destroy of Freon in a cement kiln(在水泥窑中销毁氟利昂)[J].Fore Buil Mat Trans(国外建材译丛),1997,9(1) :49-52.
[7] Gal′ A,Ogata A,Futamura S,et al.Mechanism of the dissociation of chlorofluorocarbons during nonthermal plasma processing in nitrogen at atmospheric pressure[J].J Phys Chem A,2003,107(42):8859-8866.
[8] Chen Deng-yun(陈登云),Sun Da-hai(孙大海),Ying Hai(应海),et al.Influences of Freon-12(CF2CCl2) on the electron number densities in an inductively coupled plasma (ICP) measured with Hα line-The applications of ICP in the disposal of hazardous waste(用Hα线研究Freon12 (CF2CCl2)对电感耦合等离子体(ICP)电子密度的影响-ICP技术在危险废弃物处理方面的应用研究)[J].Spectrosc Spect Anal(光谱学与光谱分析),1998,18(2):199-204.
[9] Wu Jian-ping(吴建平).Decomposition of Freon by plasma method(用等离子法分解氟利昂)[J].Cry Spec Gases(低温与特气),1990,1990(3) :53-54.
[10] Zakharenko V S,Parmon V N.Photoadsorption and photocatalytic processes affecting the composition of the Earth’s atmosphere:II.Dark and photostimulated adsorption of Freon 22 (CHF2Cl) on MgO[J].Kinet Catal,2000,41(6):756-759.
[11] Mel’nikov M Y,Baskakov D V,Feldman V I.Spectral characteristics and transformations of intermediates in irradiated Freon 11,Freon 113,and Freon 113a[J].High Energy Chem,2002,36(5):309-315
[12] Hirai K,Nagata Y,Maeda Y.Decomposition of chlorofluorocarbons and hydrofluorocarbons in water by ultrasonic irradiation[J].Ultrason Sonochem,1996,3(3):S205-S207.
[13] Pinnock S,Hurley M D,Shine K P,et al.Radiative forcing of climate by hydrochlorofluorocarbons and hydrofluorocarbons[J].J Geophys Res Atmos,1995,100(D11):23227-23238.
[14] Zhang Jian-jun(张建君),Xu Mao-qian(许茂乾).Studies on catalytic hydrogenation of CFC-12(CFC-12的催化加氢研究) [J].J Ningxia Univer:Nat Sci Edit(宁夏大学学报(自然科学版) ),2001,22(2):211-212.
[15] Nagata H,Takakura T,Tashiro S,et al.Catalytic oxidative decomposition of chlorofluorocarbons (CFCs) in the presence of hydrocarbons[J].Appl Catal B:Environ,1994,5(1/2):23-31.
[16] Lin Yong-da(林永达),Chen Qing-yun(陈庆云).Atmospheric ozone layer depletion and CFCs alternatives (大气臭氧层破坏和CFCs替代物)[J].Prog Chem(化学进展),1998,10(2) :228-235.
[17] Hou Jian(侯健),Han Gong-yuan(韩功元),Zhang Zhen-man(张振满),et al.Atmospheric degradation of CFC-12 by dielectric barrier discharge(氟利昂-12的常压DBD降解)[J].J Fudan Univer:Nat Sci Edit(复旦学报(自然科学版)),1999,38(6):627-630
[18] Gao Hong(高红).Study on Freon-12 premixed combustion hydrolysis(昆明理工大学博士论文)[D].Kunming Univer Sci Techno(昆明理工大学),2011.
[19] Zou Jin-bao(邹金宝).Study on decomposition of CFC-12 by molten alkali (salt)(昆明理工大学博士论文)[D].Kunming Univ Sci Techno(昆明理工大学),2009.
[20] Zhao Guang-qin(赵光琴),Jia Li-juan(贾丽娟),Tang Guang-yang(唐光阳),et al.Catalytic hydrolysis of CHC1F2 and CC12F2 by ZrO2 /TiO2 solid acid catalyst(TiO2/ZrO2固体酸催化水解CHC1F2和CC12 F2的研究)[J].Environ Engineer(环境工程),2017,35(S1):138-140.
[21] Ma Zhen(马臻),Hua Wei-ming(华伟明),Tang Yi(唐颐),et al.A novel catalyst WO3/A12O3 for decomposition of CFC-12(用以分解氟利昂-12的新型催化剂WO3/A12O3)[J].Chin J Appl Chem(应用化学),2000,17(3):319-321.
[22] Ma Zhen,Hua Weiming,Tang Yi,et al.A novel CFC-12 hydrolysis catalyst:WO3/SnO2[J].Chin Chem Lett,2000,11(1):87-88.
[23] Ma Zhen,Hua Wei-ming,Tang Yi,et al.Catalytic decomposition of CFC-12 over heteropolyacids[J].Chin J Catal,2000,21(1):3-4.
[24] Ma Zhen,Hua Wei-ming,Tang Yi,et al.Catalytic decomposition of CFC-12 over on solid acids SO42-/MxOy(M=Zr,Ti,Sn,Fe,Al)[J].Chin J Chem,2000,18(3):341-345.
[25] Ma Zhen,Hua Wei-ming,Tang Yi,et al.Catalytic hydrolysis of CFC-12 over solid acid Ti(SO4)2[J].Chin Chem Lett,2000,11(4):311-314.
[26] Hua Wei-ming,Zhang Feng,Ma Zhen,et al.Catalytic hydrolysis of chlorofluorocarbon (CFC-12) over WO3/ZrO2[J].Catal Lett,2000,65(1):85-89.
[27] Hua Wei-ming,Zhang Feng,Ma Zhen,et al.WO3/ZrO2 strong acid as a catalyst for the decomposition of chlorofluorocarbon (CFC-12) [J].Chem Res Chin Univer,2000,16(2):185-187
[28] Zheng Shu-jun(郑淑君).Solid base catalysts and its application(固体碱催化剂及其应用)[J].Chem Propell Polym Mater(化学推进剂与高分子材料),2001,2001(4):18-21.
[29] Li Xiang-zhao(李向召),Jiang Qi(江琦).Progress in catalysts for solid base(固体碱催化剂研究进展)[J].Nat Gas Chem Indus(天然气化工),2005,30(1):42-48.
[30] Lu Xiao-yong(鲁晓勇),Bao De-yan(鲍德艳),Su Ming-hua(苏明华).Study on the application of magnetic solid base catalyst in the preparation of biodiesel from palm oil(磁性固体碱催化剂在棕榈油制备生物柴油中的应用研究)[J].Pet Process Petrochem (石油炼制与化工),2008,39(8):55-58.
[31] Liu Chang(刘畅),Yan Fang(颜芳),Luo Wen(罗文),et al.Nano-magnetic solid basic catalyst for producing biodiesel(纳米磁性固体碱催化剂用于合成生物柴油的研究)[J].Mod Chem Indus(现代化工),2009,29(S2):167-171.
[32] Wang Huan-huan(王欢欢),Pang Dan-dan(庞丹丹),Zheng Yao(郑尧),et al.Biodiesel production from animal fat gutter oil by MgO /ZrO2 solid base catalyst(MgO-ZrO2固体碱催化废弃动物油制备生物柴油)[J].Chin J Environ Engineer(环境工程学报),2016,10(3):1484-1491.
[33] Liu Tian-cheng(刘天成).Study on ZrO2-based solid acid-base catalytic hydrolysis of low concentration Freon(昆明理工大学博士论文)[D].Kunming Univ Sci Techno(昆明理工大学),2010.
[34] Liu T C,Ning P,Wang H B,et al.Catalytic hydrolysis of CCl2F2 over solid base CaO/ZrO2 [J].Adv Mater Res,2013,652/654:1533-1538.
[35] Liu T C,Ning P,Wang H B,et al.Catalytic decomposition of CCl2F2 over solid base Na2O/ZrO2 [J].Adv Mater Res,2013,634/638:494-499.
[36] Liu T C,Guo Y J,Tang G Y,et al.Adsorption thermodynamics study on CCl2F2 over solid base Na2O/ZrO2 [J].Appl Mech Mater,2014,457/458:112-115.
[37] Zou Jin-bao(邹金宝),Ning Ping(宁平),Gao Hong(高红),et al.Study on combustion hydrolyzing technology in treating CFCs(氟利昂的燃烧水解法处理研究)[J].J Kunming Univer Sci Technol:Sci Technol Edit(昆明理工大学学报(理工版)),2009,34(1):92-94.
[38] Taltita Y,Wakamatsu H,Tokumaru M,et al.Decomposition of chlorofluorocarbons over metal phosphate ca- talysts Part III.Reaction path of CC12F2 decomposition over AlPO4[J].Appl Catal A:General,2000,194/195:55-61.
[39] Hattori H.Solid base catalysts:generation of basic sites and application to organic synthesis[J].Appl Catal A:Gener,2001,222:247-259.
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