碱土金属氧化物催化裂解酸化油及动力学研究

doi:10.3969/j.issn.1673-5854.2022.02.006

Abstract

Abstract:

Alkaline earth metal oxides(MgO, CaO and BaO) were used as cracking catalysts, and a 3L cracking reactor made in the laboratory was used to crack and deoxidize acidic oil to prepare hydrocarbon fuels. The results showed that the yields of liquid fuel obtained from catalytic cracking of acidic oil by three kinds of alkaline earth metal oxides were 70%-80%; CaO and MgO as cracking catalysts could effectively deoxidize and produce more liquid fuel under lower reaction temperature and the acid value of the fuel was lower than 20 mg/g. Barium stearate, calcium stearate, and magnesium stearate was used as model compounds to study the kinetics of the pyrolysis reaction of waste oils, the thermogravimetric analysis was performed first, and then the kinetic parameters of the thermogravimetric results were calculated by using the distributed activation energy method. The results showed the pyrolysis activation energies of barium stearate, calcium stearate, and magnesium stearate decreased sequentially, which were 268, 204 and 127 kJ/mol, respectively. Above results indicated that the use of MgO as catalyst to crack acidic oil could collect more liquid fuel in the lower temperature section, and the waste oil was converted at lower temparture, which could effectively reduce the energy consumption during the conversion reaction.

Key words: acidic oil, alkaline earth metal oxides, catalytic cracking, activation energy, TG analysis

CLC Number:

TQ35

Feng LONG, Xia JIANG, Xincheng CAO, Peng LIU, Junming XU. Catalytic Cracking of Acidic Oil by Alkaline Earth Metal Oxides and Its Kinetics Study[J]. Biomass Chemical Engineering, 2022, 56(2): 33-39.

Figures/Tables 8

Fig.1

Table 1

Fig.2

Table 2

Composition of the prolysis oil by using alkaline earth metal oxides catalytic cracking acidic oil"

时间/min time	化合物名称 compound name	相对峰面积relative area/%
时间/min time	化合物名称 compound name	无催化no catalyst	MgO	CaO	BaO
7.33	癸烷decane	0.160	0.453	0.733	0.204
10.28	十一烷undecane	0.498	0.848	0.887	0.494
13.17	十二碳烯dodecene	0.331	0.830	0.899	0.580
13.51	十二烷dodecane	1.346	1.437	2.372	1.568
13.91	2, 6-二甲基-十一烷2, 6-dimethyl-undecane	—	0.320	0.654	—
14.11	十三碳烯tridecene	1.222	1.858	1.132	0.911
15.98	十三烷tridecane	5.042	0.704	1.815	3.227
16.56	十四碳烯tetradecene	1.727	0.804	3.105	2.911
17.88	1, 2-二氢-1, 1, 6-三甲基-萘1, 2-dihydro-1, 1, 6-trimethyl-naphthalene	0.472	0.487	0.749	0.710
19.14	十四烷tetradecane	2.166	2.032	2.193	2.030
21.55	十五碳烯pentadecene	2.283	1.683	1.597	1.532
21.75	十五烷pentadecane	1.452	0.710	3.214	2.892
22.73	十六烷hexadecyne	1.718	0.760	0.984	2.128
23.01	1-戊基环戊烯1-decyl-cyclopentene	0.226	—	0.876	0.863
23.16	6, 7-二甲基双环-[4.2.0]辛烷6, 7-dimethyl bicyclo-[4.2.0.]octane	—	0.750	—	—
23.50	1-壬基-环己烯1-nonyl-cyclohexene	0.800	0.956	0.824	1.203
23.84	十六烯hexadecene	0.861	0.947	0.842	0.583
24.21	十六烷hexadecane	0.587	1.332	0.984	1.753
24.92	2-甲基-双环[2.2.2]辛烷2-methyl-bicyclo[2.2.2]octane	0.102	1.927	—	0.661
25.24	7-甲基-3, 4-辛二烯7-methyl-3, 4-octadiene	—	0.273	0.671	0.264
25.88	1, 11-十二碳二烯1, 11-dodecadiene	0.092	1.956	—	—
26.03	十七碳烯8-heptadecene	3.70	5.952	2.329	4.141
26.55	十七烷heptadecane	1.280	1.386	1.514	1.204
26.69	2, 6, 11, 15-四甲基-十六烷2, 6, 11, 15-tetramethyl-hexadecane	—	0.858	1.011	0.933
27.25	1, 1, 2-三甲基环戊烷1, 1, 2-trimethyl-cycloundecane,	1.826	0.687	1.954	1.848
27.51	1, 2, 3-三甲基环己烷1, 2, 3-trimethyl-cyclohexane	3.581	1.433	3.15	3.248
28.36	十一烷基-苯undecyl-benzene	0.475	—	0.734	0.384
28.44	1-甲基十九烷基-苯1-methylnonadecyl-benzene	—	0.558	0.664	—
28.45	1-甲基癸基-苯1-methyldecyl-benzene	0.242	0.880	0.514	0.165
28.78	十八烷octadecane	0.441	2.972	0.810	2.173
28.98	3, 8-二甲基-癸烷3, 8-dimethyl-decane	—	3.185	—	—
29.49	3, 7, 11, 15-四甲基-2-十六烯3, 7, 11, 15-tetramethyl-2-hexadecene	0.605	0.871	0.718	0.659

Table 2

Table 3

Fig.3

Fig.4

Table 4

References 19

1	LONG F , ZHAI Q L , LIU P , et al. Catalytic conversion of triglycerides by metal-based catalysts and subsequent modification of molecular structure by ZSM-5 and Raney Ni for the production of high-value biofuel[J]. Renewable Energy, 2020, 157, 1072- 1080. doi: 10.1016/j.renene.2020.05.117
2	张永辉, 闵永军, 徐俊明. 车用典型生物燃料的组分及理化特性对比研究[J]. 新能源进展, 2018, 6 (6): 461- 466. doi: 10.3969/j.issn.2095-560X.2018.06.001
3	杨飞, 陈伟, 张晨, 等. 活塞式航空发动机燃用生物航煤与RP-3燃料的适用性对比[J]. 生物质化学工程, 2019, 53 (6): 15- 21. doi: 10.3969/j.issn.1673-5854.2019.06.003
4	LONG F , LI F L , ZHAI Q L , et al. Thermochemical conversion of waste acidic oil into hydrocarbon products over basic composite catalysts[J]. Journal of Cleaner Production, 2019, 234, 105- 112. doi: 10.1016/j.jclepro.2019.06.109
5	XU J M , LONG F , JIANG J C , et al. Integrated catalytic conversion of waste triglycerides to liquid hydrocarbons for aviation biofuels[J]. Journal of Cleaner Production, 2019, 222, 784- 792. doi: 10.1016/j.jclepro.2019.03.094
6	徐俊明, 肖国民, 周永红, 等. 油脂热化学转化制备可再生液体燃料油研究进展[J]. 化工进展, 2011, 30 (7): 1456- 1460.
7	CHEN W H , LIN B J , HUANG M Y , et al. Thermochemical conversion of microalgal biomass into biofuels: A review[J]. Bioresource Technology, 2015, 184, 314- 327. doi: 10.1016/j.biortech.2014.11.050
8	LI L X , COPPOLA E , RINE J , et al. Catalytic hydrothermal conversion of triglycerides to non-ester biofuels[J]. Energy & Fuels, 2010, 24 (2): 1305- 1315.
9	刘玉环, 刘英语, 王允圃, 等. 油脂催化裂解制备可再生烃类燃料研究进展[J]. 化工进展, 2013, 32 (11): 2588- 2592.
10	胡慧敏, 韩艳辉, 郭琳, 等. 植物油脂转化制备燃料油技术研究进展[J]. 山西化工, 2017, 37 (3): 33- 37.
11	LI F L , JIANG J C , LIU P , et al. Catalytic cracking of triglycerides with a base catalyst and modification of pyrolytic oils for production of aviation fuels[J]. Sustainable Energy & Fuels, 2018, 2 (6): 1206- 1215.
12	XU J M , JIANG J C , LU Y J , et al. Liquid hydrocarbon fuels obtained by the pyrolysis of soybean oils[J]. Bioresource Technology, 2009, 100 (20): 4867- 4870. doi: 10.1016/j.biortech.2009.04.055
13	XU J M , JIANG J C , SUN Y J , et al. Production of hydrocarbon fuels from pyrolysis of soybean oils using a basic catalyst[J]. Bioresource Technology, 2010, 101 (24): 9803- 9806. doi: 10.1016/j.biortech.2010.06.147
14	LONG F, ZHANG X L, CAO X C, et al. Mechanism investigation on the formation of olefins and paraffin from the thermochemical catalytic conversion of triglycerides catalyzed by alkali metal catalysts[J/OL]. Fuel Processing Technology, 2020, 200: 106312[2021-01-10]. https://doi.org/10.1016/j.fuproc.2019.106312.
15	MIURA K , MAKI T . A simple method for estimating f(E) and k₀(E) in the distributed activation energy model[J]. Energy Fuels, 1998, 12 (5): 864- 869. doi: 10.1021/ef970212q
16	VÁRHEGYI G , BOBÁLY B , JAKAB E , et al. Thermogravimetric study of biomass pyrolysis kinetics.A distributed activation energy model with prediction tests[J]. Energy Fuels, 2011, 25 (1): 24- 32. doi: 10.1021/ef101079r
17	张旭, 孙姣, 范赢, 等. 芦苇秆热解特性及动力学分析[J]. 生物质化学工程, 2019, 53 (4): 9- 18.
18	刘旭光, 李保庆. 分布活化能模型的理论分析及其在半焦气化和模拟蒸馏体系中的应用[J]. 燃料化学学报, 2001, 29 (1): 54- 59. doi: 10.3969/j.issn.0253-2409.2001.01.011
19	赵岩, 邱朋华, 谢兴, 等. 煤热解动力学分布活化能模型适用性分析[J]. 煤炭转化, 2017, 40 (1): 13- 18. doi: 10.3969/j.issn.1004-4248.2017.01.003

催化剂 catalyst	不同温度段下液体产物得率/% yield of liquid products at different temperatures						液体燃料酸值/ (mg·g^-1) acid number	水/% water	残炭/% coke	气体/% gas
催化剂 catalyst	0~350 ℃	350~370 ℃	370~390 ℃	390~410 ℃	410~430 ℃	430~450 ℃	液体燃料酸值/ (mg·g^-1) acid number	水/% water	残炭/% coke	气体/% gas
BaO	2.3	6.9	14.3	30.6	25.8	1.9	64.8	1.9	7.9	8.4
CaO	5.8	8.3	20.5	16.4	10.8	9.2	15.1	4.4	13.7	10.9
MgO	7.4	15.2	21.3	13.5	6.8	7.6	17.3	4.3	8.2	15.7

催化剂 catalyst	烷烃alkanes		烯烃 alkenes	芳香烃 aromatics	炔烃 alkynes	其他 others
催化剂 catalyst	直链烃paraffins	环烷烃cycloalkanes	烯烃 alkenes	芳香烃 aromatics	炔烃 alkynes	其他 others
BaO	18.9	8.7	28.6	4.3	1.2	38.4
CaO	19.4	10.4	35.2	3.2	0.7	28.1
MgO	12.7	12.7	30.4	4.0	2.3	27.9

模型化合物 model compound	转化率 conversion rate	活化能(E)/(kJ·mol^-1) reaction activation energy	指前因子(A)/min^-1 pre-finger factor	相关系数(R²) correlation coefficient
硬脂酸钡 barium stearate	0.1	178	3.80×10³	0.9709
	0.2	245	1.16×10⁴	0.9928
	0.3	261	4.98×10⁴	0.9963
	0.4	266	9.76×10⁴	0.9976
	0.5	301	2.57×10⁴	0.9999
	0.6	312	4.12×10⁴	0.9999
	0.7	316	2.58×10⁴	0.9883
硬脂酸钙 calcium stearate	0.1	208	1.37×10⁹	0.9657
	0.2	177	4.10×10⁶	0.9771
	0.3	197	1.61×10⁶	0.9651
	0.4	167	1.06×10⁵	0.9740
	0.5	170	3.21×10⁴	0.9864
	0.6	174	6.08×10⁴	0.9865
	0.7	176	2.00×10⁴	0.9929
	0.8	275	3.78×10⁹	0.9979
	0.9	291	1.05×10¹¹	0.9489
硬脂酸镁 magnesium stearate	0.1	114	5.93×10⁵	0.9992
	0.2	119	1.67×10⁹	0.9956
	0.3	122	1.42×10¹⁰	0.9957
	0.4	135	2.17×10¹⁰	0.9997
	0.5	125	2.24×10¹⁰	0.9957
	0.6	138	1.39×10¹¹	0.9997
	0.7	128	1.86×10¹¹	0.9991
	0.8	129	3.88×10⁹	0.9916
	0.9	131	2.56×10¹⁰	0.9911

[1]	Shengchao DAI, Deqing MEI, Weidong ZHAO, Dengpan ZHANG. Catalytic Cracking of Coconut Oil for Biofuel Production [J]. Biomass Chemical Engineering, 2022, 56(2): 19-26.
[2]	Yang LI, Kai LI, Zhenxi ZHANG, Shiyu FENG, Bin HU, Qiang LU. Research Progress on Catalytic Pyrolysis of Biomass with Alkaline Earth Metal Oxide-based Catalysts [J]. Biomass Chemical Engineering, 2021, 55(6): 39-48.
[3]	Dongyang HE, Guowei LIANG, Xinyang LI, Shuangyi WU, Miaomiao NIU. Research Review on Cracking and Removal of Tar Catalyzed by Biomass Coke [J]. Biomass Chemical Engineering, 2021, 55(4): 77-84.
[4]	FAN Fangyu, HUANG Yuanbo, YANG Xiaoqin, ZHENG Yunwu, LIU Can, WANG Zhen, ZHENG Zhifeng. Pyrolysis Characteristics and Kinetics of Shells Biomass [J]. bce, 2018, 52(6): 8-14.
[5]	YANG Nannan, ZHAO Rongxuan, LIU Liansheng, DUAN Runze, CHEN Shangshang. Grape Branches Pyrolysis and Gasification Characteristic in Flue Gas Atmosphere [J]. bce, 2018, 52(4): 17-22.
[6]	HU Bing-tao, LI Zhi-jian. Pyrolysis Characteristics and Kinetics of Guanzhong Wheat Straw Using TG-FT-IR [J]. bce, 2016, 50(2): 6-12.
[7]	LI Dong-mei;LI Qian;ZHAO Zhen-dong;BI Liang-wu;LIN Ke-zhong;CHEN Yu-xiang;WANG Jing;HOU Wen-biao;GU Yan. Study on Preparation of Bio-fuel Oil from Rosin Residue in Industrial Deep Processes [J]. , 2010, 44(4): 13-16.
[8]	WANG Wen-zhao;LIU Chao;TANG Jing-wen. Compensation Effect and an Improved Computing Method of Kinetic Parameters [J]. , 2008, 42(4): 13-16.
[9]	LI Jun-xiong. Preparation of Biodiesel from Oils with High Acid Value [J]. , 2007, 41(6): 25-28.
[10]	NIE Xiao-an;JIANG Jian-chun;ZHANG Tian-jian;ZHU Jin-hua. Pilot Study on Preparation Technique of Biodiesel and Chemical Products [J]. , 2007, 1(1): 1-4.
[11]	NIE Xiao-an;JIANG Jian-chun;ZHANG Tian-jian;ZHU Jin-hua. Pilot Study on Preparation Technique of Biodiesel and Chemical Products [J]. , 2007, 41(1): 1-4.

Catalytic Cracking of Acidic Oil by Alkaline Earth Metal Oxides and Its Kinetics Study

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 8

References 19

Related Articles 11

Recommended Articles

Metrics

Comments