钙磷比对钌/磷灰石催化氧化二氯甲烷性能的影响

万继国; 徐力; 王钰

doi:10.13205/j.hjgc.202501019

钙磷比对钌/磷灰石催化氧化二氯甲烷性能的影响

doi: 10.13205/j.hjgc.202501019

万继国¹,
徐力^1,2,,
王钰^1,

1. 武汉科技大学资源与环境工程学院, 武汉 430081;
2. 汕尾市创新工业设计研究院, 广东汕尾 516600

基金项目:

武汉科技大学“十四五”湖北省优势特色学科(群)项目(2023A0302)

广东省普通高校重点领域专项(2021ZDZX4094,2023ZDZX3091)

详细信息

作者简介:
万继国(1998-),男,硕士研究生,主要研究方向为磷灰石基催化剂制备及其VOCs催化氧化性能。

通讯作者:
徐力(1986-),男,副研究员,主要研究方向为多相催化。xuli3021@gmail.com
王钰(1986-),男,副教授,主要研究方向为固废资源化及环境催化应用。yuwang@wust.edu.cn

徐力(1986-),男,副研究员,主要研究方向为多相催化。xuli3021@gmail.com
王钰(1986-),男,副教授,主要研究方向为固废资源化及环境催化应用。yuwang@wust.edu.cn

计量
- 文章访问数: 11
- HTML全文浏览量: 3
- PDF下载量: 0
- 被引次数: 0
出版历程
- 收稿日期: 2023-10-09
- 录用日期: 2024-03-27
- 修回日期: 2024-01-02
- 网络出版日期: 2025-03-21
- 刊出日期: 2025-03-21

Effect of Ca/P ratio on catalytic oxidation of dichloromethane over Ru/hydroxyapatite catalysts

WAN Jiguo¹,
XU Li^{1,2
,},
WANG Yu^1
,

1. College of Resources and Environment Engineering, Wuhan University of Science and Technology, Wuhan 430081, China;
2. Shanwei Innovation Industrial Design & Research Institute, Shanwei 516600, China

摘要

摘要: 采用液相沉积法制备了一系列含有不同钙磷摩尔比的羟基磷灰石[HAP(X),X为n(Ca)/n(P)],通过尿素均相沉积沉淀法将钌(Ru)负载于HAP(X)表面,制得Ru/HAP(X)催化剂。由XRD、FT-IR、SEM、TEM、H₂-TPR、NH₃-TPD等表征结果可知:Ru纳米颗粒在HAP表面呈高度分散状态,Ru/HAP(1.67)表现出最佳的低温氧化还原性能,同时具有最丰富的中、强酸性位点。以二氯甲烷(DCM)为典型含氯挥发性有机物(CVOCs),考察了Ru/HAP(X)对DCM催化氧化活性、选择性和稳定性,结果表明:Ru/HAP(1.67)对DCM催化氧化性能最好,且稳定性良好。钙磷摩尔比对DCM反应副产物的分布有显著影响,Ru/HAP(1.50)由于酸性较强,检测到不完全分解产物CH₃Cl,随着钙磷摩尔比增加,Ru/HAP(1.60)和Ru/HAP(1.67)则以CHCl₃和CCl₄为主要副产物。研究成果可为CVOCs催化氧化工业应用和磷资源高附加值利用提供参考。
- 二氯甲烷 /
- 羟基磷灰石 /
- 催化氧化 /
- 钌 /
- 酸性位
Abstract: Catalytic oxidation is the most effective way to treat CVOCs. At present, the core difficulties in making efficient CVOCs catalysts are achieving high activity, resistance to chlorine poisoning and resistance to high temperature sintering. In this experiment, a series of hydroxyapatite (HAP(X), X refers to the Ca/P molar ratio) with different Ca/P molar ratios were prepared by liquid phase deposition method, and then ruthenium (Ru) was loaded on the surface of HAP(X) by urea homogeneous deposition precipitation method to prepare the Ru/HAP(X) catalyst. As shown by the results of XRD, FT-IR, SEM, TEM, H₂-TPR, NH₃-TPD, etc., Ru nanoparticles were highly dispersed on the surface of HAP, and Ru/HAP(1.67) exhibited the best low-temperature reducibility, as well as the richest medium and strong acid sites. The catalytic oxidation activity, selectivity, and stability of Ru/HAP(X) for dichloromethane (DCM) were investigated by taking DCM as typical chlorine-containing VOCs. The investigation result indicated that Ru/HAP(1.67) had the best catalytic oxidation performance and good stability for DCM. The Ca/P molar ratio had a significant effect on the distribution of by-products in the DCM reaction. Monochloromethane, an incomplete decomposition product, was detected in Ru/HAP (1.50) because of its strong acidity. With the increase in Ca/P molar ratio, trichloromethane and tetrachloromethane were the main by-products of Ru/HAP(1.60) and Ru/HAP(1.67). The research results provide references for industrial application of CVOCs catalytic oxidation and high value-added utilization of phosphorus resources.
- dichloromethane /
- hydroxyapatite /
- catalytic oxidation /
- ruthenium /
- acid site

HTML全文

参考文献(35)

[1]	席劲瑛,武俊良,胡洪营,等. 工业VOCs排放源废气排放特征调查与分析[J]. 中国环境科学, 2010, 30(11): 1558-1562. XI J Y, WU J L, HU H Y, et al. Investigation and analysis of exhaust gas emission characteristics of industrial VOCs emission sources[J]. China Environmental Science, 2010, 30(11): 1558-1562.
[2]	陈立,刘霄龙,施文博,等. 氯代挥发性有机物CVOCs催化氧化的研究进展[J]. 环境工程, 2017, 35(10): 114-119. CHEN L, LIU X L, SHI W B, et al. Research progress in catalytic oxidation of chlorinated volatile organic compounds (CVOCs)[J]. Environmental Engineering, 2017, 35(10): 114-119.
[3]	汤奔,苏惠旋. 化工类废气挥发性有机VOC的危害及催化氧化技术研究进展[J]. 广东化工, 2023, 50(9): 150-153. TANG B, SU H X. Research progress on the hazards of volatile organic VOCs in chemical waste gas and catalytic oxidation technology[J]. Guangdong Chemical Industry, 2023, 50(9): 150-153.
[4]	魏潇,黄胜,吴幼青,等. VOCs末端治理技术的研究现状[J]. 环境工程, 2023, 41(增刊1): 338-344. WEI X, HUANG S, WU Y Q, et al. Research status of VOCs end treatment technology[J]. Environmental Engineering, 2023 , 41(S1): 338-344.
[5]	张景才. 耐高温负载型贵金属催化燃烧及甲烷干重整催化剂研究[D]. 济南:山东大学, 2017. ZHANG J C. Research on high temperature supported catalysts for catalytic combustion of precious metals and dry reforming of methane[D]. Jinan: Shandong University, 2017.
[6]	MA M J, ZHANG Y, JI Y J, et al. Diluted silicon promoting Pd/Pt catalysts for oxygen reduction reaction with strong anti-poisoning effect[J]. Applied Catalysis B: Environmental, 2022, 315.
[7]	唐文清,冯泳兰,李小明. 掺硅碳羟基磷灰石的制备及其对Pb²⁺的吸附性能[J]. 中国环境科学, 2013, 33(6): 1017-1024. TANG W Q, FENG Y L, LI X M. Preparation of silica-doped hydroxyapatite and its adsorption properties for Pb²⁺[J]. China Environmental Science, 2013, 33(6): 1017-1024.
[8]	马利国,孙艳荣,李东来,等. 羟基磷灰石载体的结构和作用及在催化剂制备中的应用[J]. 硅酸盐学报, 2019, 47(12): 1808-1817. MA L G, SUN Y R, LI D L, et al. Structure and function of hydroxyapatite support and its application in catalyst preparation[J]. Journal of the Chinese Ceramics, 2019, 47(12): 1808-1817.
[9]	SHUAI C J, YANG W J, FENG P, et al. Accelerated degradation of HAP/PLLA bone scaffold by PGA blending facilitates bioactivity and osteoconductivity[J]. Bioactive Materials, 2021, 6(2): 490-502.
[10]	李梦雨,汤建伟,刘咏,等. 醋酸酸解磷尾矿制备醋酸钙镁融雪剂工艺研究[J]. 无机盐工业, 2024, 56(1): 73-80. LI M Y, TANG J W, LIU Y, et al. Study on preparation of calcium and magnesium acetate snowmelt from tailings of phosphorous solution[J]. Inorganic Chemicals Industry, 2024, 56(1): 73-80.
[11]	刘羽,钟康年,胡文云. 钙磷比对溶—凝法合成羟基磷灰石特征的影响[J]. 化学工业与工程技术, 1997(1): 20-22,56. LIU Y, ZHONG K N, HU W Y. Effect of the ratio of calcium and phosphorus on the characteristics of hydroxyapatite synthesized by solution-coagulation method[J]. Chemical Industry and Engineering Technology, 1997(1): 20-22,56.
[12]	WANG J D,LIU J K, LU Y, et al. Catalytic performance of gold nanoparticles using different crystallinity HAP as carrier materials[J]. Materials Research Bulletin, 2014, 55.
[13]	TRUNG B C, TU L N Q, THANH L D, et al. Combined adsorption and catalytic oxidation for low-temperature toluene removal using nano-sized noble metal supported on ceria-granular carbon[J]. Journal of Environmental Chemical Engineering, 2020, 8(2).
[14]	YANG P, YANG S S, SHI Z N, et al. Deep oxidation of chlorinated VOCs over CeO₂ based transition metal mixed oxide catalysts[J]. Applied Catalysis B: Environmental, 2015, 162.
[15]	戴晓霞. 铈基催化剂催化净化氯苯的反应机制及性能优化研究[D]. 杭州:浙江大学, 2020. DAI X X. Reaction mechanism and optimization of the ceria-based catalysts in the catalytic destruction of chlorobenzene[D]. Hangzhou:Zhejiang University,2020.
[16]	XIAO M L, YANG X Q, PENG Y, et al. Confining shell-sandwiched Ag clusters in MnO₂-CeO₂ hollow spheres to boost activity and stability of toluene combustion[J]. Nano Research, 2022, 15(8).
[17]	SHEN K, GAO B, XIA H Q, et al. Oxy-anionic doping: a new strategy for improving selectivity of Ru/CeO₂ with synergetic versatility and thermal stability for catalytic oxidation of chlorinated volatile organic compounds[J]. Environmental Science & Technology, 2022.
[18]	WANG Y, YANG D, LI S, et al. Ru/hierarchical HZSM-5 zeolite as efficient bi-functional adsorbent/catalyst for bulky aromatic VOCs elimination[J]. Microporous and Mesoporous Materials, 2018, 258.
[19]	施文博. 钌基催化剂催化氧化VOCs的研究进展[J]. 化工技术与开发, 2016, 45(8): 36-38. SHI W B.Research Progress of Catalytic Oxidation of VOCs with Ru-based Catalyst[J]. Technology & Development of Chemical Industry,2016,45(8):36-38.
[20]	孙海杰,刘欣改,陈志浩,等. 羟基磷灰石负载Ru催化氨硼烷产氢性能研究[J]. 江西师范大学学报(自然科学版), 2020, 44(4): 424-428. SUN H J,LIU X G,CHEN Z H,et al. The Performance of Ru/HAP Catalysts for Hydrogen Generation from Catalytic Hydrolysis of Ammonia Borane[J]. Journal of Jiangxi Normal University( Natural Science), 2020, 44(4): 424-428.
[21]	BROWN P W, CONSTANTZ B. Hydroxyapatite and Related Materials[M]. Boca Raton: CRC Press.
[22]	SALMA K, BERZINA-C L, BORODAJENKO N. Calcium phosphate bioceramics prepared from wet chemically precipitated powders[J]. Processing and Application of Ceramics, 2010, 4(1): 45-51.
[23]	MATSUURA Y, ONDA A, YANAGISAWA K. Selective conversion of lactic acid into acrylic acid over hydroxyapatite catalysts[J]. Catalysis Communications, 2014, 48.
[24]	LIN G B, LIN W W, WU J H, et al. Oxidation of 5-methoxymethylfurfural to 2, 5-furandicarboxylic acid over Ru/hydroxyapatite catalyst in water[J]. Chemical Engineering Science, 2022, 249.
[25]	GUO X Y, LIU B, GAO X H, et al. Improved olefin selectivity during CO hydrogenation on hydrophilic Fe/HAP catalysts[J]. Catalysis Today, 2023, 410.
[26]	WANG Y, WANG P, LU X F, et al. Construction of mesoporous Ru@ZSM-5 catalyst for dichloromethane degradation: synergy between acidic sites and redox centres[J]. Fuel, 2023, 346.
[27]	WANG Y, DU C, LIU Z, et al. Highly active and durable chlorobenzene oxidation catalyst via porous atomic layer coating of Ru on Pt/Al₂O₃[J]. Applied Catalysis B: Environmental, 2023, 330.
[28]	ZHANG Y P, LI G B, WU P, et al. Enhancement of PdV/TiO₂ catalyst for low temperature DCM catalytic removal and chlorine poisoning resistance by oxygen vacancy construction[J]. Chemical Engineering Science, 2022, 264: 118126.
[29]	SILVESTER L, LAMONIER J F, VANNIER R N, et al. Structural, textural and acid-base properties of carbonate-containing hydroxyapatites[J]. Journal of Materials Chemistry A, 2014, 2(29).
[30]	DAI Q G, SHEN K, DENG W, et al. HCl-tolerant H_xPO₄/RuO_x-CeO₂ catalysts for extremely efficient catalytic elimination of chlorinated VOCs[J]. Environmental Science & Technology, 2021, 55(6).
[31]	WANG Y, CHEN Y, ZHANG L, et al. Total catalytic oxidation of chlorinated aromatics over bimetallic Pt-Ru supported on hierarchical HZSM-5 zeolite[J]. Microporous and Mesoporous Materials, 2020, 308.
[32]	DAI Q G, BAI S, WANG X, et al. Catalytic combustion of chlorobenzene over Ru-doped ceria catalysts: mechanism study[J]. Applied Catalysis B: Environmental, 2013, 129: 580-588.
[33]	TESCHNER D, FARRA R, YAO L, et al. An integrated approach to Deacon chemistry on RuO₂-based catalysts[J]. J Catal, 2012, 285(1): 273-284.
[34]	LIN F W, ZHANG Z M, LI N, et al. How to achieve complete elimination of Cl-VOCs: a critical review on byproducts formation and inhibition strategies during catalytic oxidation[J]. Chemical Engineering Journal, 2021, 404: 126534.
[35]	SU J, YAO W Y, LIU Y, et al. The impact of CrO_x loading on reaction behaviors of dichloromethane (DCM) catalytic combustion over Cr-O/HZSM-5 catalysts[J]. Applied Surface Science, 2017, 396.