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

生物质化学工程 ›› 2022, Vol. 56 ›› Issue (2): 33-39.doi: 10.3969/j.issn.1673-5854.2022.02.006

碱土金属氧化物催化裂解酸化油及动力学研究

龙锋¹, 蒋霞¹, 曹新诚¹, 刘朋¹, 徐俊明¹^,²^,*()

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2021-02-01 出版日期:2022-03-30 发布日期:2022-03-25
通讯作者: 徐俊明 E-mail:xujunming@icifp.cn
作者简介:徐俊明, 研究员, 博士生导师, 研究领域: 生物质能源与材料; E-mail: xujunming@icifp.cn
龙锋(1995—), 男, 江西宜春人, 硕士生, 从事生物质先进液体燃料的研究
基金资助:
中国林业科学研究院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2018QC001)

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

Feng LONG¹, Xia JIANG¹, Xincheng CAO¹, Peng LIU¹, Junming XU¹^,²^,*()

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2021-02-01 Online:2022-03-30 Published:2022-03-25
Contact: Junming XU E-mail:xujunming@icifp.cn

摘要/Abstract

摘要：

以碱土金属氧化物(MgO、CaO和BaO)作为裂解催化剂, 在实验室自制的3 L裂解反应釜中对酸化油进行裂解脱氧制备烃类燃油。结果显示: 3种碱土金属氧化物催化裂解酸化油所得液体燃油产率为70%~80%, 特别是CaO和MgO作为裂解催化剂能够有效地脱氧, 能够在较低的温度下获得更多的液体燃油, 同时燃油的酸值低于20 mg/g。以硬脂酸钡、硬脂酸钙、硬脂酸镁为模型化合物研究废弃油脂裂解反应动力学, 先进行热重分析, 再利用分布活化能法对热重结果进行动力学参数计算, 结果表明: 硬脂酸钡、硬脂酸钙、硬脂酸镁的裂解活化能依次降低, 分别为268, 204和127 kJ/mol。以上结果表明: 用MgO催化裂解酸化油能够在较低温度下收集更多的液体燃油, 从而在较低温度下实现废弃油脂的裂解转化, 有效降低反应能耗。

关键词: 酸化油, 碱土金属氧化物, 催化裂解, 活化能, 热重分析

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

中图分类号:

TQ35

龙锋, 蒋霞, 曹新诚, 刘朋, 徐俊明. 碱土金属氧化物催化裂解酸化油及动力学研究[J]. 生物质化学工程, 2022, 56(2): 33-39.

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.

图/表 8

图1

表1

图2

表2

碱土金属氧化物催化裂解酸化油的主要组分分析"

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

表2

表3

图3

图4

表4

参考文献 19

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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

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碱土金属氧化物催化裂解酸化油及动力学研究

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

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