12-磷钨酸插层MgAl水滑石的合成、表征及催化酯化原油脱酸性能

吴雁; 雷艳清; 刘新月; 邱月; 王豪

12-磷钨酸插层MgAl水滑石的合成、表征及催化酯化原油脱酸性能

西南石油大学化学化工学院, 四川成都 610500

基金项目:

国家自然科学基金 21506176

详细信息

中图分类号: O643.3
计量
- 文章访问数: 86
- HTML全文浏览量: 47
- PDF下载量: 11
- 被引次数: 0
出版历程
- 收稿日期: 2017-05-12
- 修回日期: 2017-07-13
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-09-10

Synthesis and characterization of 12-tungstophosphoric acid intercalated MgAl layered double hydroxides and their application as esterification catalysts for deacidification of crude oil

School of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China

Funds:

National Natural Science Foundation of China 21506176

More Information

Corresponding author: WANG Hao, E-mail:wpuwanghao1216@sina.com

摘要

摘要: 采用离子交换法合成了不同Mg/Al物质的量比的12-磷钨酸（H₃PW₁₂O₄₀，HPW）插层水滑石（LDHs），采用XRD、FT-IR、Raman、ICP-AES、TG-DSC等分析手段表征其物化性质，Hammett指示剂-正丁胺滴定法测定其酸强度和酸量分布。进一步将其用于原油催化酯化脱酸反应，并与NO₃型LDHs对比，探讨酯化活性与催化剂性质之间的关系。结果表明，催化剂的活性主要受酸性和比表面积的影响。HPW插层LDHs的酯化活性明显优于NO₃型LDHs，归因于增强的酸性和增大的比表面积。对于弱酸性的NO₃型LDHs，酯化活性与比表面积呈正向关系，Mg/Al物质的量比为4时，具有最大的比表面积和脱酸活性。而对于较强酸性的HPW插层LDHs，酯化活性主要受到酸量的影响，Mg/Al物质的量比为2的催化剂具有最高的酸量和脱酸活性。
- 12-磷钨酸 /
- 水滑石 /
- 酯化 /
- 脱酸
Abstract: 12-tungstophosphoric acid (H₃PW₁₂O₄₀, HPW) intercalated layered double hydroxides (LDHs) with various Mg/Al molar ratios were synthesized by an ion-exchange method. The samples were characterized by XRD, FT-IR, Raman, ICP-AES and TG-DSC. The acid strength and amount of acidic sites of catalysts were measured by Hammett indicator and n-butylamine titration technique. Furthermore, HPW intercalated LDHs were used as esterification catalysts for deacidification of crude oil and compared with their nitrate LDHs precursors. The relationship between the catalytic activity and the property of HPW intercalated LDHs was investigated. It is found that the catalytic activity of LDHs mainly depends on the acidity and the specific surface area. HPW intercalated LDHs exhibit a much higher catalytic activity than nitrate LDHs owing to the increased acidity and specific surface area. Due to the poorer acidity, the activity of nitrate LDHs is proportional to their specific surface area. The nitrate LDH with Mg/Al molar ratio of 4 exhibits the highest specific surface area and deacidification ratio. However, for highly acidic HPW intercalated LDHs, the amount of acidic sites dominates the catalytic activity and the HPW intercalated LDH with Mg/Al molar ratio of 2 has the highest acidity and esterification activity.
- 12-tungstophosphoric acid /
- layered double hydroxides /
- esterification /
- deacidification

HTML全文

图 1 MgAl-x-NO₃和MgAl-x-PW的XRD谱图

Figure 1 XRD patterns of MgAl-x-NO₃ and MgAl-x-PW

下载: 全尺寸图片幻灯片

图 2 MgAl-2-NO₃、MgAl-x-PW和HPW的FT-IR谱图

Figure 2 FT-IR spectra of MgAl-2-NO₃, MgAl-x-PW and HPW

下载: 全尺寸图片幻灯片

图 3 MgAl-x-PW和HPW的Raman谱图

Figure 3 Raman spectra of MgAl-x-PW and HPW

下载: 全尺寸图片幻灯片

图 4 MgAl-3-NO₃和MgAl-3-PW的TG-DSC曲线

Figure 4 TG-DSC curves of MgAl-3-NO₃ and MgAl-3-PW

下载: 全尺寸图片幻灯片

图 5 反应温度对脱酸率的影响

Figure 5 Effect of reaction temperature on deacidification ratio under the conditions of 20g oil, 0.2g catalyst, 0.6mL ethylene glycol and 2h

下载: 全尺寸图片幻灯片

图 6 反应时间对脱酸率的影响

Figure 6 Effect of reaction time on deacidification ratio under the conditions of 20g oil, 0.2g catalyst, 0.6mL ethylene glycol and 180℃

下载: 全尺寸图片幻灯片

图 7 乙二醇用量对脱酸率的影响

Figure 7 Effect of EG dosage on deacidification ratio under the conditions of 20g oil, 0.2g catalyst, 2h and 180℃

下载: 全尺寸图片幻灯片

表 1 HPW和MgAl-x-PW的吸收峰归属

Table 1 Adsorption band assignment of HPW and MgAl-x-PW

Sample	Wavenumber σ/cm^-1
Sample	ν(P-O_a)	ν (W=O_t)	ν(W-O_c-W)	ν(W-O_e-W)
HPW	1080	985	892	800
MgAl-2-PW	1065	961	905	793
MgAl-3-PW	1068	959	895	807
MgAl-4-PW	1069	958	893	812
MgAl-5-PW	1071	952	884	816

下载: 导出CSV

表 2 MgAl-x-PW的元素组成和分子式

Table 2 Elemental composition and formulae of MgAl-x-PW

Sample	Elemental composition w/%				Molar ratio	Formula
Sample	Mg	Al	W	P	Mg/Al	Formula
MgAl-2-PW	3.19	2.31	62.16	0.88	1.56	Mg_0.61Al_0.39(OH)₂(PW₁₂O₄₀)_0.13·mH₂O
MgAl-3-PW	4.72	2.27	62.03	0.84	2.32	Mg_0.71Al_0.30(OH)₂(PW₁₂O₄₀)_0.10·mH₂O
MgAl-4-PW	6.11	2.24	53.48	0.75	3.09	Mg_0.74Al_0.24(OH)₂(PW₁₂O₄₀)_0.07·mH₂O
MgAl-5-PW	7.65	2.23	38.76	0.53	3.86	Mg_0.76Al_0.20(OH)₂(PW₁₂O₄₀)_0.04·mH₂O

下载: 导出CSV

表 3 MgAl-x-NO₃和MgAl-x-PW的酸性、比表面积和脱酸活性

Table 3 Acidic property, specific surface area and deacidification ratio of MgAl-x-NO₃ and MgAl-x-PW

Sample	Acid strength(H₀)	Amount of acidic sites /(mmol·g^-1)	Percentage of mid-strong acidic sites /%	Specific surface area A/(m²·g^-1)	Deacidification ratio /%
MgAl-2-NO₃	4.8≤ H₀≤7.2	0.16	-	10.97	30.8
MgAl-3-NO₃	4.8≤ H₀≤7.2	0.13	-	15.52	37.5
MgAl-4-NO₃	4.8≤ H₀≤7.2	0.12	-	40.88	41.9
MgAl-5-NO₃	4.8≤ H₀≤7.2	0.06	-	11.58	36.8
	0.8≤ H₀≤7.2	0.65
MgAl-2-PW	3.86≤ H₀≤4.8	0.20	36.92	34.88	81.6
	0.8≤ H₀≤3.86	0.04
	0.8≤ H₀≤7.2	0.61
MgAl-3-PW	3.86≤ H₀≤4.8	0.18	34.43	52.89	73.4
	0.8≤ H₀≤3.86	0.03
	0.8≤ H₀≤7.2	0.57
MgAl-4-PW	3.86≤ H₀≤4.8	0.15	29.82	57.91	66.2
	0.8≤ H₀≤3.86	0.02
	0.8≤ H₀≤7.2	0.50
MgAl-5-PW	3.86≤ H₀≤4.8	0.11	22.00	83.61	62.6
	0.8≤ H₀≤3.86	-

下载: 导出CSV

参考文献(31)

[1]	陈清涛, 朱玉龙, 秦一鸣, 田义斌. 国内外高酸原油脱酸发展现状[J]. 当代化工, 2014, 43(6): 1053-1055. http://d.wanfangdata.com.cn/Periodical/ddhg201406061 CHEN Qing-tao, ZHU Yu-long. Development status of high acid crude oil deacidification technologies[J]. Contemp Chem Ind, 2014, 43(6):1053-1055. http://d.wanfangdata.com.cn/Periodical/ddhg201406061
[2]	谢丽, 张伟, 李子锋, 慕旭宏.超声波在高酸原油酯化脱酸中的应用研究[J].石油炼制与化工, 2010, 41(1):6-10. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201001005.htm XIE Li, ZHANG Wei, LI Zi-feng, MU Xu-hong. Study on the application of ultrasonic in the esterification deacidification of high acid crude oil[J]. Pet Process Petrochem, 2010, 41(1):6-10. http://www.cnki.com.cn/Article/CJFDTOTAL-SYLH201001005.htm
[3]	段雪, 张法智.插层组装与功能材料[M].北京:化学工业出版社, 2007. DUAN Xue, ZHANG Fa-zhi. Intercalation Assembly and Functional Materials[M]. Beijing:Chemistry Industry Press, 2007.
[4]	吴雁, 闫琛洋, 王豪.镁铝水滑石催化酯化原油脱酸研究[J].石油与天然气化工, 2009, 38(2):129-131. http://www.cnki.com.cn/Article/CJFDTOTAL-STQG200902013.htm WU Yan, YAN Cheng-yang, WANG Hao. Study on the esterification reaction for removing the acids from crude oil using Mg-Al hydroxides as catalyst[J]. Chem Eng Oil Gas, 2009, 38(2):129-131. http://www.cnki.com.cn/Article/CJFDTOTAL-STQG200902013.htm
[5]	吴雁, 王豪, 钟婷, 张灵, 胥利蛟.不同方法合成的镁铝水滑石的表征及其催化原油酯化脱酸性能[J].石油学报(石油加工), 2011, 27(5):687-693. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201105006.htm WU Yan, WANG Hao, ZHONG Ting, ZHANG Ling, XU Li-jiao. Characterization of Mg-Al hydroxides prepared by various methods and their catalytic activities for esterification to remove acid from crude oil[J]. Acta Petrol Sin (Pet Process Section), 2011, 27(5):687-693. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG201105006.htm
[6]	LI X, ZHU J, LIU Q, WU B. The removal of naphthenic acids from dewaxed VGO via esterification catalyzed by Mg-Al hydrotalcite[J]. Fuel Process Technol, 2013, 111:68-77. doi: 10.1016/j.fuproc.2013.01.016
[7]	黄延召, 朱建华, 王艳艳, 武本成.锌铝类水滑石催化酯化高酸原油脱酸[J].中国石油大学学报:自然科学版, 2010, 34(6):147-150. http://www.cnki.com.cn/Article/CJFDTOTAL-SYDX201006030.htm HUANG Yan-zhao, ZHU Jian-hua, WANG Yan-yan, WU Cheng-ben. Removal of naphthenic acids from high acid crude oil through catalytic esterification on zinc aluminum hydrotalcite-like compounds[J]. J China Univ Pet, Ed Nat Sci, 2010, 34(6):147-150. http://www.cnki.com.cn/Article/CJFDTOTAL-SYDX201006030.htm
[8]	HUANG Y, ZHU J, WU B, WANG Y. Esterification kinetics of cyclohexanecarboxylic acid and ethylene glycol in diesel oil with or without a ZnAl-HTlc catalyst[J]. Pet Sci Technol, 2011, 29(21):2209-2219. doi: 10.1080/10916461003610371
[9]	LI X, WU B, ZHU J, TAO X. Tracking catalytic esterification of naphthenic acids in crude oil by ESI FT-ICR MS[J]. China Pet Process Petrochem Technol, 2016, 18(3):57-65. http://d.wanfangdata.com.cn/Periodical/zgsyjgysyhgjs201603009
[10]	黄延召, 朱建华, 武本成, 王艳艳. ZnMgAl-HTlc催化酯化高酸原油脱酸[J].石油学报(石油加工), 2009, 25(5):731-735. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG200905021.htm HUANG Yan-shao, Zhu Jian-hua, Wu Ben-cheng, Wang Yan-yan. Catalytic esterification deacidification of the crude oil with high naphthenic acid content by ZnMgAl-HTlc[J]. Acta Petrol Sin (Pet Process Section), 2009, 25(5):731-735. http://www.cnki.com.cn/Article/CJFDTOTAL-SXJG200905021.htm
[11]	黄延召, 朱建华, 武本成, 王艳艳.高酸原油酯化脱酸催化剂的制备和性能[J].化学反应工程与工艺, 2009, 25(3):210-215. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY200903005.htm HUANG Yan-shao, Zhu Jian-hua, Wu Ben-cheng, Wang Yan-yan. Preparation ang performance of the catalyst for esterification deacidification of crude oil with high naphthenic acid number[J]. Chem React Eng Technol, 2009, 25(3):210-215. http://www.cnki.com.cn/Article/CJFDTOTAL-HXFY200903005.htm
[12]	刘洁莹, 马向荣, 党睿, 李建, 张智芳. Zn-Ni-Al-LDHs催化剂的制备及其催化酯化高酸原油脱酸[J].工业催化, 2014, 22(7):555-558. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH201407020.htm LIU Jie-ying, MA Xiang-rong, DANG Rui, LI Jian, ZHANG Zhi-fang. Preparation of Zn-Ni-Al-LDHs catalysts and their performance for removal of naphthenic acids from high acid crude oil through catalytic esterification[J]. Ind Catal, 2014, 22(7):555-558. http://www.cnki.com.cn/Article/CJFDTOTAL-GYCH201407020.htm
[13]	马向荣, 李健, 党睿, 高雯雯, 李霄, 屈媛. Ni-Mg-Al-LDHs的制备及其催化酯化高酸原油脱酸的研究[J].应用化工, 2013, 42(1):30-32. http://www.cnki.com.cn/Article/CJFDTOTAL-SXHG201301010.htm MA Xiang-rong, LI Jian, DANG Rui, GAO Wen-wen, Li Xiao, QU Yuan. Preparation of Ni-Mg-Al-LDHs materials and removal of naphthenic acids from high acid crude oil through catalytic esterification on Ni-Mg-Al-LDHs[J]. Appl Chem Ind, 2013, 42(1):30-32. http://www.cnki.com.cn/Article/CJFDTOTAL-SXHG201301010.htm
[14]	王恩波, 胡长文.多酸化学导论[M].北京:化学工业出版社, 1998. WANG En-bo, HU Chang-wen. Introduction of Polyacid Chemistry[M]. Beijing:Chemistry Industry Press, 1998.
[15]	DAS J, PARIDA K M. Heteropoly acid intercalated Zn/Al HTlc as efficient catalyst for esterification of acetic acid using n-butanol[J]. J Mol Catal A:Chem, 2007, 264(1/2):248-254. http://www.sciencedirect.com/science/article/pii/S1381116906012362
[16]	谢美芳, 郑建华.磷钨酸柱撑水滑石催化合成乙酸正丁酯的研究[J].化学与生物工程, 2010, 27(5):42-44. http://www.cnki.com.cn/Article/CJFDTOTAL-HBHG201005017.htm XIE Mei-fang, Zheng Jian-hua. Study on synthesis of n-butyl acetate catalyzed by Phosphato-Tungstic heteropolyacid pillar double hydroxides[J]. Chem Bioeng, 2010, 27(5):42-44. http://www.cnki.com.cn/Article/CJFDTOTAL-HBHG201005017.htm
[17]	WANG H, DUAN W, WU Y, TANG Y, LI L. Synthesis of magnesium-aluminum layered double hydroxide intercalated with ethylene glycol by the aid of alkoxides[J]. Inorg Chim Acta, 2014, 418(1):163-170. http://www.sciencedirect.com/science/article/pii/S0020169314002369?via=sd
[18]	CAVANI F, TRIFIRÒ F, VACCARI A. Hydrotalcite-type anionic clays:Preparation, properties and applications[J]. Catal Today, 1991, 11(2):173-301. doi: 10.1016/0920-5861(91)80068-K
[19]	YANG Q Z, SUN D J, ZHANG C G, WANG X J, ZHAO W A. Synthesis and characterization of polyoxyethylene sulfate intercalated Mg-Al-nitrate layered double hydroxide[J]. Langmuir, 2003, 19(14):5570-5574. doi: 10.1021/la034526j
[20]	于凤丽. 基于多酸阴离子功能化的主客体型催化剂的燃油深度脱硫研究[D]. 济南: 山东大学, 2013. http://d.wanfangdata.com.cn/Thesis/Y2433701 YU Feng-Li. Study on deep desulfurization of fuel oil with the heteropolyacid anion as functional building block in host-guest type composite catalyst[D]. Jinan:Shandong University, 2013. http://d.wanfangdata.com.cn/Thesis/Y2433701
[21]	LI Z, YOU J, WANG J, YANG P, JING X, ZHANG M. Synthesis and characterization of tungstophosphoric acid intercalated Ni/Al HTlc with magnetite[J]. J Mater Process Technol, 2009, 209(5):2613-2619. doi: 10.1016/j.jmatprotec.2008.06.005
[22]	WEIR M R, KYDD R A. Synthesis of heteropolyoxometalate-pillared Mg/Al, Mg/Ga, and Zn/Al layered double hydroxides via LDH-hydroxide precursors[J]. Inorg Chem, 1998, 37(21):5619-5624. doi: 10.1021/ic9805067
[23]	DUAN X, EVANS D G. Layered double hydroxides[M]. Berlin:Springer, 2006.
[24]	刘继广, 郭军, 孙铁.杂多阴离子柱撑水滑石类层柱材料中层柱相互作用研究[J].高等学校化学学报, 1995, 16(9):1329-1333. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH509.001.htm LIU Ji-Guang, Guo Jun, Sun Tie. Studies on the interaction between the layers and pillars of hydrotalcite-like compounds pillared with heteropolyanions[J]. Chem J Chinese U, 1995, 16(9):1329-1333. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH509.001.htm
[25]	CALIMAN E, DIAS J A, DIAS S C L, PRADO A G S. Solvent effect on the preparation of H₃PW₁₂O₄₀ supported on alumina[J]. Catal Today, 2005, 107-108(44):816-825.
[26]	李小磊, 蒋平平, 卢云, 张伟杰, 董玉明. 12-磷钨杂多酸根柱撑水滑石合成及催化脂肪酸甲酯环氧化[J].化学学报, 2012, 70(5):544-550. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB201205005.htm LI Xiao-Lei, JIANG Ping-ping, LU Yun, ZHANG Wei-jie, DONG Yu-ming. Synthesis of hydrotalcite-like compounds intercalcated by 12-phosphorous tungsten heteropoly acid and catalytic performance on the epoxidation of fatty acid methyl esters[J]. Acta Chim Sinica, 2012, 70(5):544-550. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB201205005.htm
[27]	郭军, 矫庆泽, 沈剑平, 吕慧娟, 刘丹, 蒋大振, 闵恩泽.杂多阴离子柱撑水滑石的合成、热稳定性、酸碱性研究[J].化学学报, 1996, 54(4):357-362. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB199604007.htm GUO Jun, JIAO Qing-ze, SHEN Jian-ping, LU Hui-juan, LIU Dan, JIANG Da-zhen, MIN En-ze. Studies on synthesis, thermal stabilities and acid-base properities of heteropolyanions pillared layered double hydroxides[J]. Acta Chim Sinica, 1996, 54(4):357-362. http://www.cnki.com.cn/Article/CJFDTOTAL-HXXB199604007.htm
[28]	LUO Q S, LI L, WANG Z X, DUAN X. Theoretical study of the layer-anion interactions in magnesium aluminum layered double hydroxides[J]. Chinese J Inorg Chem, 2001, 17(6):835-842. http://en.cnki.com.cn/Article_en/CJFDTOTAL-WJHX200106011.htm
[29]	CANTRELL D G, GILLIE L J, LEE A F, WILSON K. Structure-reactivity correlations in MgAl hydrotalcite catalysts for biodiesel synthesis[J]. Appl Catal A Gen, 2005, 287(2):183-190. doi: 10.1016/j.apcata.2005.03.027
[30]	JIA Y, FANG Y, ZHANG Y, MIRAS H N, SONG Y F. Classical Keggin intercalated into layered double hydroxides:Facile preparation and catalytic efficiency in Knoevenagel condensation reactions[J]. Chem Eur J, 2015, 21(42):14862-14870. doi: 10.1002/chem.201501953
[31]	舒庆, 侯小鹏, 刘峰生, 唐国强, 许宝泉, 张彩霞.稀土镧改性磷钨杂多酸盐催化油酸与甲醇酯化反应合成生物柴油活性研究[J].有色金属科学与工程, 2016, 7(3):131-136. http://www.cnki.com.cn/Article/CJFDTOTAL-JXYS201603023.htm SHU Qing, HOU Xiao-peng, LIU Feng-sheng, TANG Guo-qiang, XU Bao-quan, ZHANG Cai-xia. Catalytic activity of La-modified phosphotungstic heteropoly acid salt in synthesis of biodiesel from esterification of methanol and oleci acid[J]. Nonferrous Met Sci Eng, 2016, 7(3):131-136. http://www.cnki.com.cn/Article/CJFDTOTAL-JXYS201603023.htm