废木油与石油沥青相容机制的分子动力学研究

doi:10.11949/0438-1157.20230656

摘要/Abstract

摘要：

借助分子动力学(MD)方法，构建了AAA-1沥青分子模型、4种不同废木油(WWO)改性剂掺量的生物沥青模型及其对应的4种WWO分子模型等9种体系，并验证了上述模型的有效性，基于微观指标分析了温度和改性剂掺量对WWO与石油沥青之间相容性的影响机制。结果表明：WWO与石油沥青的内聚能密度(CED)和溶解度参数均随温度的升高而逐渐减小；非键合与范德华相互作用能更适合作为WWO与石油沥青之间相互作用的评价指标；石油沥青与生物沥青的原子径向分布函数(RDF)曲线峰值位置(1.11 Å)大致相同，且峰高随着WWO的添加而略有下降；自由体积分数(FFV)会随着探针半径的增大而减小，随着温度的升高而增大，且加入WWO后，FFV总体呈现减小趋势，但在某些条件下会出现一定程度的增大。据此推荐WWO改性剂的掺量为10%。

关键词: 分子模拟, 生物质, 热力学性质, 植物基生物沥青, 相容性, 分子间相互作用

Abstract:

With the help of molecular dynamics (MD) method, 9 systems including AAA-1 asphalt molecular model, 4 bio-asphalt models with different waste wood oil (WWO) modifier content and their corresponding 4 WWO molecular models were constructed. The validity of the above model was verified, and the influence mechanism of temperature and modifier dosage on the compatibility between WWO and petroleum asphalt was analyzed based on microscopic indicators. The results show that the cohesive energy density (CED) and solubility parameters of both WWO and petroleum asphalt indicated a downward trend as the temperature rises. The non-bonding and van der Waals interaction energy were more suitable as evaluation indicators for the interaction between WWO and petroleum asphalt. Furthermore, the petroleum asphalt and bio-asphalts showed similar radial distribution function (RDF) peaks at around 1.11 Å, and the peak height decreased slightly due to the addition of WWO. The free volume fraction (FFV) will decrease as the probe radius increases and increase as the temperature increases. After adding WWO, the FFV generally shows a decreasing trend, but under certain conditions there will be a certain degree of increase. Therefore, it is recommended that the mass fraction of the WWO modifier is 10%.

Key words: molecular simulation, biomass, thermodynamic properties, plant-based bio-asphalt, compatibility, intermolecular interaction

中图分类号:

TE 626

郑直, 郭乃胜, 尤占平, 王家伟. 废木油与石油沥青相容机制的分子动力学研究[J]. 化工学报, 2023, 74(10): 4037-4050.

Zhi ZHENG, Naisheng GUO, Zhanping YOU, Jiawei WANG. Research on compatibility mechanisms between waste wood oil and petroleum asphalt through molecular dynamics[J]. CIESC Journal, 2023, 74(10): 4037-4050.

图/表 21

参考文献 45

1	Lv S T, Liu J, Peng X H, et al. Laboratory experiments of various bio-asphalt on rheological and microscopic properties[J]. Journal of Cleaner Production, 2021, 320: 128770.
2	徐宁, 汪海年, 陈玉, 等. 基于分子动力学的生物沥青相容性研究[J]. 华南理工大学学报(自然科学版), 2022, 50(5): 65-72.
	Xu N, Wang H N, Chen Y, et al. Research on the compatibility of bio-asphalt based on molecular dynamics[J]. Journal of South China University of Technology (Natural Science Edition), 2022, 50(5): 65-72.
3	Sun Z J, Yi J Y, Huang Y D, et al. Properties of asphalt binder modified by bio-oil derived from waste cooking oil[J]. Construction and Building Materials, 2016, 102: 496-504.
4	Gao J F, Wang H N, You Z P, et al. Rheological behavior and sensitivity of wood-derived bio-oil modified asphalt binders[J]. Applied Sciences, 2018, 8(6): 919.
5	Meng Y Y, Zhan L, Hu C C, et al. Research on modification mechanism and performance of an innovative bio-based polyurethane modified asphalt: a sustainable way to reducing dependence on petroleum asphalt[J]. Construction and Building Materials, 2022, 350: 128830.
6	Dong Z J, Zhou T, Luan H, et al. Composite modification mechanism of blended bio-asphalt combining styrene-butadiene-styrene with crumb rubber: a sustainable and environmental-friendly solution for wastes[J]. Journal of Cleaner Production, 2019, 214: 593-605.
7	Yao X G, Li C X, Xu T. Multi-scale studies on interfacial system compatibility between asphalt and SBS modifier using molecular dynamics simulations and experimental methods[J]. Construction and Building Materials, 2022, 346: 128502.
8	Tang J, Wang H, Liang M. Molecular simulation and experimental analysis of interaction and compatibility between asphalt binder and styrene-butadiene-styrene[J]. Construction and Building Materials, 2022, 342: 128028.
9	Gao M X, Chen Y L, Fan C H, et al. Molecular dynamics study on the compatibility of asphalt and rubber powder with different component contents[J]. ACS Omega, 2022, 7(41): 36157-36164.
10	丛玉凤, 廖克俭, 翟玉春.分子模拟在SBS改性沥青中的应用[J]. 化工学报, 2005, 56(5): 769-773.
	Cong Y F, Liao K J, Zhai Y C. Application of molecular simulation for study of SBS modified asphalt[J]. Journal of Chemical Industry and Engineering (China), 2005, 56(5): 769-773.
11	Huang T, Zhang Z P, Wang L, et al. Study on the compatibility between polyurethane and asphalt based on experiment and molecular dynamics simulation[J]. Case Studies in Construction Materials, 2022, 17: e01424.
12	Feng L, Zhao P, Chen T D, et al. Comparative study of octavinyl oligomeric sesquisiloxane nanomaterial-modified asphalt using molecular dynamics method[J]. Polymers, 2022, 14(21): 4577.
13	Feng L, Zhao P, Chen T D, et al. Study on the influence of nano-OvPOSS on the compatibility, molecular structure, and properties of SBS modified asphalt by molecular dynamics simulation[J]. Polymers, 2022, 14(19): 4121.
14	丁鹤洋, 汪海年, 徐宁, 等. 基于分子动力学的生物质油改性沥青相容性研究[J]. 材料导报, 2023, 37(2): 248-255.
	Ding H Y, Wang H N, Xu N, et al. Study on compatibility of biomass oil modified asphalt binder based on molecular dynamics[J]. Materials Reports, 2023, 37(2): 248-255.
15	屈鑫, 丁鹤洋, 王超, 等. 基于分子动力学模拟技术的生物质油改性沥青微观性能研究[J].材料导报, 2022, 36(19): 124-129.
	Qu X, Ding H Y, Wang C, et al. Study on micro-properties of biomass oil modified asphalt based on molecular dynamics simulation technology[J]. Materials Reports, 2022, 36(19): 124-129.
16	Hildebrand J H. Dipole attraction and hydrogen bond formation in their relation to solubility[J]. Science, 1936, 83(2141): 21-24.
17	Faasen D P, Jarray A, Zandvliet H J W, et al. Hansen solubility parameters obtained via molecular dynamics simulations as a route to predict siloxane surfactant adsorption[J]. Journal of Colloid and Interface Science, 2020, 575: 326-336.
18	Lu P Z, Ma Y H, Ye K, et al. Analysis of high-temperature performance of polymer-modified asphalts through molecular dynamics simulations and experiments[J]. Construction and Building Materials, 2022, 350: 128903.
19	Li D D, Greenfield M L. Chemical compositions of improved model asphalt systems for molecular simulations[J]. Fuel, 2014, 115: 347-356.
20	Ding H Y, Wang H N, Qu X, et al. Towards an understanding of diffusion mechanism of bio-rejuvenators in aged asphalt binder through molecular dynamics simulation[J]. Journal of Cleaner Production, 2021, 299: 126927.
21	Khabaz F, Khare R. Molecular simulations of asphalt rheology: application of time-temperature superposition principle[J]. Journal of Rheology, 2018, 62(4): 941-954.
22	Zhou T, Kabir S F, Cao L P, et al. Effects of ultraviolet exposure on physicochemical and mechanical properties of bio-modified rubberized bitumen: sustainability promotion and resource conservation[J]. Resources, Conservation and Recycling, 2021, 171: 105626.
23	Dong Z J, Zhou T, Luan H, et al. Performance evaluation of bio-based asphalt and asphalt mixture and effects of physical and chemical modification[J]. Road Materials and Pavement Design, 2020, 21(6): 1470-1489.
24	Zheng X W, Xu W Y, Xu H P, et al. Research on the ability of bio-rejuvenators to disaggregate oxidized asphaltene nanoclusters in aged asphalt[J]. ACS Omega, 2022, 7(25): 21736-21749.
25	Chen W X, Chen S, Zheng C F. Analysis of micromechanical properties of algae bio-based bio-asphalt-mineral interface based on molecular simulation technology[J]. Construction and Building Materials, 2021, 306: 124888.
26	Gao J F, Wang H N, You Z P, et al. Research on properties of bio-asphalt binders based on time and frequency sweep test[J]. Construction and Building Materials, 2018, 160: 786-793.
27	Jiao B Z, Pan B F, Che T K. Evaluating impacts of desulfurization and depolymerization on thermodynamics properties of crumb rubber modified asphalt through molecular dynamics simulation[J]. Construction and Building Materials, 2022, 323: 126360.
28	Zhu X Y, Du Z, Ling H W, et al. Effect of filler on thermodynamic and mechanical behaviour of asphalt mastic: a MD simulation study[J]. International Journal of Pavement Engineering, 2020, 21(10): 1248-1262.
29	张家康. 基于流变学与分子动力学方法的复合改性沥青的相互作用行为与触变性研究[D]. 成都: 西南交通大学, 2021.
	Zhang J K. Study on interaction behavior and thixotropy of composite modified asphalt based on rheology and molecular dynamics methods[D]. Chengdu: Southwest Jiaotong University, 2021.
30	Li C X, Fan S Y, Xu T. Method for evaluating compatibility between SBS modifier and asphalt matrix using molecular dynamics models[J]. Journal of Materials in Civil Engineering, 2021, 33(8): 04021207.
31	Ding Y J, Tang B M, Zhang Y Z, et al. Molecular dynamics simulation to investigate the influence of SBS on molecular agglomeration behavior of asphalt[J]. Journal of Materials in Civil Engineering, 2015, 27(8): C4014004.
32	Guo F C, Zhang J P, Pei J Z, et al. Investigating the interaction behavior between asphalt binder and rubber in rubber asphalt by molecular dynamics simulation[J]. Construction and Building Materials, 2020, 252: 118956.
33	丁勇杰. 基于分子模拟技术的沥青化学结构特征研究[D]. 重庆: 重庆交通大学, 2013.
	Ding Y J. Study on chemical structure characteristics of asphalt based on molecular simulation technology[D]. Chongqing: Chongqing Jiaotong University, 2013.
34	林智. 再生沥青微观性能及其与矿料界面交互行为研究[D]. 长春: 吉林大学, 2023.
	Lin Z. Study on microscopic properties of recycled asphalt and its interface interaction with mineral aggregate interface[D]. Changchun: Jilin University, 2023.
35	Li G N, Tan Y Q, Fu Y K, et al. Density, zero shear viscosity and microstructure analysis of asphalt binder using molecular dynamics simulation[J]. Construction and Building Materials, 2022, 345: 128332.
36	Li L, Xin C, Guan M Y, et al. Using molecular dynamics simulation to analyze the feasibility of using waste cooking oil as an alternative rejuvenator for aged asphalt[J]. Sustainability, 2021, 13(8): 4373.
37	Liu J Z, Yu B, Hong Q Z. Molecular dynamics simulation of distribution and adhesion of asphalt components on steel slag[J]. Construction and Building Materials, 2020, 255: 119332.
38	He L, Li G N, Lv S T, et al. Self-healing behavior of asphalt system based on molecular dynamics simulation[J]. Construction and Building Materials, 2020, 254: 119225.
39	Sun B, Zhou X X. Diffusion and rheological properties of asphalt modified by bio-oil regenerant derived from waste wood[J]. Journal of Materials in Civil Engineering, 2018, 30(2): 04017274.
40	Sun W, Wang H. Molecular dynamics simulation of diffusion coefficients between different types of rejuvenator and aged asphalt binder[J]. International Journal of Pavement Engineering, 2020, 21(8): 966-976.
41	徐珊, 王晶博, 陆阿定, 等. 蓝藻和松木热解液化制取生物油的试验研究[J]. 可再生能源, 2014, 32(9): 1371-1378.
	Xu S, Wang J B, Lu A D, et al. Experimental research on preparation of bio-oil by cyanobacteria and pine pyrolysis liquefaction[J]. Renewable Energy Resources, 2014, 32(9): 1371-1378.
42	Zheng W H, Wang H N, You Z P, et al. Mechanism and rheological characterization of MDI modified wood-based bio-oil asphalt[J]. Construction and Building Materials, 2021, 309: 125113.
43	曾梦澜, 田伟, 朱艳贵, 等. 蓖麻油生物沥青调和沥青混合料使用性能研究[J]. 湖南大学学报(自然科学版), 2017, 44(11): 177-182.
	Zeng M L, Tian W, Zhu Y G, et al. Study on performance of castor oil-based bioasphalt blended asphalt mixture[J]. Journal of Hunan University (Natural Sciences), 2017, 44(11): 177-182.
44	Lu P Z, Huang S M, Shen Y, et al. Mechanical performance analysis of polyurethane-modified asphalt using molecular dynamics method[J]. Polymer Engineering & Science, 2021, 61(9): 2323-2338.
45	曹雪娟, 苏玥, 邓梅. 基于分子动力学模拟的聚合物改性剂与沥青相互作用研究[J]. 化工新型材料, 2021, 49(9): 234-239.
	Cao X J, Su Y, Deng M. Investigation on interaction between polymer modifier and asphalt based on molecular dynamics simulation[J]. New Chemical Materials, 2021, 49(9): 234-239.

材料	热力学判据	计算结果	试验/模拟结果
石油沥青	密度 (298 K, 1 atm)/(g·cm^-3)	0.997	0.95~1.04^[35-36]
	CED_total/(10⁸ J·m^-3)	3.219	3.19~3.32^[28,37]
	δ/(J·cm^-3)^1/2	17.931	17.55^[38], 17.628^[39], 18.10^[40]
WWO	密度 (298 K, 1 atm)/(g·cm^-3)	1.059	1.09^[41], 1.10^[42]
	CED_total/(10⁸ J·m^-3)	4.331	—
	δ/(J·cm^-3)^1/2	21.060	21.25^[2]
生物沥青	密度 (298 K, 1 atm)/(g·cm^-3)	1.001	0.99^[43], 1.04^[25]
	CED_total/(10⁸ J·m^-3)	3.272	—
	δ/(J·cm^-3)^1/2	18.086	—

材料	热力学判据	计算结果	试验/模拟结果
石油沥青	密度 (298 K, 1 atm)/(g·cm^-3)	0.997	0.95~1.04^[35-36]
	CED_total/(10⁸ J·m^-3)	3.219	3.19~3.32^[28,37]
	δ/(J·cm^-3)^1/2	17.931	17.55^[38], 17.628^[39], 18.10^[40]
WWO	密度 (298 K, 1 atm)/(g·cm^-3)	1.059	1.09^[41], 1.10^[42]
	CED_total/(10⁸ J·m^-3)	4.331	—
	δ/(J·cm^-3)^1/2	21.060	21.25^[2]
生物沥青	密度 (298 K, 1 atm)/(g·cm^-3)	1.001	0.99^[43], 1.04^[25]
	CED_total/(10⁸ J·m^-3)	3.272	—
	δ/(J·cm^-3)^1/2	18.086	—

温度/K	CED_total/ （J·cm^-3)	CED_vdW/ （J·cm^-3)	CED_ele/ （J·cm^-3)	CED_other/ （J·cm^-3)
373	294.900	277.600	2.030	15.250
393	286.700	269.800	1.920	14.950
413	280.400	264.100	1.706	14.66
433	273.400	257.100	1.855	14.410
453	266.100	250.500	1.415	14.150

温度/K	CED_total/ （J·cm^-3)	CED_vdW/ （J·cm^-3)	CED_ele/ （J·cm^-3)	CED_other/ （J·cm^-3)
373	294.900	277.600	2.030	15.250
393	286.700	269.800	1.920	14.950
413	280.400	264.100	1.706	14.66
433	273.400	257.100	1.855	14.410
453	266.100	250.500	1.415	14.150

温度/K	δ_vdW/ （J·cm^-3)^1/2	δ_ele/ （J·cm^-3)^1/2	δ_other/ （J·cm^-3)^1/2	δ_Hansen/ （J·cm^-3)^1/2
373	16.657	1.418	3.905	17.167
393	16.420	1.380	3.866	16.925
413	16.243	1.279	3.828	16.737
433	16.028	1.337	3.795	16.525
453	15.818	1.172	3.761	16.301