椰子油催化裂解制备生物燃料的研究

doi:10.3969/j.issn.1673-5854.2022.02.004

摘要/Abstract

摘要：

以椰子油为原料, 通过液相裂解法和气相催化裂解法制备高品位的生物燃料。在温度450 ℃、进气速率30 mL/min、反应时间45 min的液相裂解条件下, 椰子油液相裂解的液体产率达到最大为76.5%, 但裂解液酸值较高, 在100 mg/g以上。为了降低裂解液酸值, 以纳基膨润土为载体, CaO作为催化剂, 对液相裂解产物之一的裂解液进行气相催化裂解。研究结果表明: 在温度400 ℃、催化剂CaO用量15%的条件下, 椰子油气相催化裂解的液体产率峰值为69.5%, 酸值为26.8 mg/g; 在温度450 ℃、催化剂CaO用量30%的条件下, 椰子油气相催化裂解的液体产率为64.1%, 酸值为2.8 mg/g, 此时酸值最低。经GC-MS分析可知, 液相裂解液中主要包含烃类、酮类和酸类等组分, 其质量分数分别为32.6%、24.2%和43.3%, 而气相催化裂解液中烃类物质增加23.3个百分点, 不利的酸、酮类物质则分别降低18.8和4.6个百分点。与椰子油相比, 液相裂解的液体产物运动黏度与含氧量降低, 酸值与低位热值升高; 与液相裂解液相比, 气相催化裂解的液体产物的酸值与含氧量降低, 热值升高。经气相催化裂解得到的生物燃料和0#柴油更为接近。

关键词: 生物燃料, 液相裂解, 气相催化裂解, 催化剂, 酸值

Abstract:

High-grade biofuels were produced from coconut oil through liquid phase cracking(LPC) and gas phase catalytic cracking(GPCC). With LPC of coconut oil, the maximum biofuel yield reached 76.5% under the pyrolysis temperature of 450 ℃, intake rate of 30 mL/min and reaction time of 40 min. However, the acid value of biofuel was above 100 mg/g. Thus the GPCC processing craft of pyrolysis liquid which was one of the cracking products was constructed with the CaO/bentonit as combined catalyst to reduce the acid value. The results showed that the maximum yield rate of biofuel reached 69.5% under the pyrolysis temperature of 400 ℃ and CaO dosage of 15% in the combined catalyst, and the acid value of the biofuel was 26.8 mg/g. Meanwhile, the minimum acid value of biofuel was 2.8 mg/g under the pyrolysis temperature of 450 ℃ and CaO dosage of 30% in the combined catalyst, and the yield of biofuel reached 64.1%. Through GC-MS analysis, it could be known that the major components in the liquid product via LPC were hydrocarbons, ketones, and acids, and their mass fractions were 32.6%, 24.2% and 43.3%, respectively. Compared with former, the hydrocarbons in GPCC liquid products increased by 23.3 percentage points, and the unfavorable acids and ketones decreased by 18.8 and 4.6 percentage points, respectively. The kinematic viscosity and oxygen content of biofuel obtained from the LPC of coconut oil decreased, while the acid value and low calorific value increased. Furthermore, the GPCC biofuel had lower acid value, lower oxygen content and higher calorific value than those of the LPC biofuel. As a whole, the GPCC biofuel had more similar properties with 0# diesel compared with the LPC biofuel.

Key words: biofuel, liquid phase cracking, gas phase catalytic cracking, catalyst, acid value

中图分类号:

TQ35
S216.2

代圣超, 梅德清, 赵卫东, 张登攀. 椰子油催化裂解制备生物燃料的研究[J]. 生物质化学工程, 2022, 56(2): 19-26.

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.

图/表 7

图1

图2

图3

图4

图5

表1

表2

参考文献 17

1	高虎. "双碳"目标下中国能源转型路径思考[J]. 国际石油经济, 2021, (3): 6.
2	BAJPAI P . Biomass to Energy Conversion Technologies[M]. Amsterdam: Elsevier, 2020: 169- 173.
3	IRFAN M , ZHAO Z Y , PANJWANI M K , et al. Assessing the energy dynamics of Pakistan: Prospects of biomass energy[J]. Energy Reports, 2019, 6, 80- 93.
4	HARDY J . A greener future with biodiesel[J]. Green Chemistry, 2001, 3 (4): G56- G58.
5	WANG W C , THAPALIYA N , CAMPOS A A , et al. Hydrocarbon fuels from vegetable oils via hydrolysis and thermo-catalytic decarboxylation[J]. Fuel, 2012, 95, 622- 629. doi: 10.1016/j.fuel.2011.12.041
6	权克静. 生物油脂的催化裂解反应研究[D]. 青岛: 青岛科技大学, 2013.
7	TRABELSI A B H , ZAAFOURI K , BAGHDADI W , et al. Second generation biofuels production from waste cooking oil via pyrolysis process[J]. Renewable Energy, 2018, 126, 888- 896. doi: 10.1016/j.renene.2018.04.002
8	章国栋. 熔盐裂解油脂制备生物燃料[D]. 杭州: 浙江工业大学, 2014.
9	ABDELFATTAH M S H , ABU-ELYAZEED O S M , EBTSAM A E M , et al. On biodiesels from castor raw oil using catalytic pyrolysis[J]. Energy, 2018, 143, 950- 960. doi: 10.1016/j.energy.2017.09.095
10	UTTAMAPRAKROM W , REUBROYCHAROEN P , VITIDSANT T , et al. Catalytic degradation of rapeseed(Brassica napus) oil to a biofuel using MgO: An optimization and kinetic study[J]. Journal of the Japan Institute of Energy, 2017, 96 (6): 190- 198. doi: 10.3775/jie.96.190
11	SIRAJUDIN N , JUSOFF K , YANI S , et al. Biofuel production from catalytic cracking of palm oil[J]. World Applied Sciences Journal, 2013, 26 (26): 67- 71.
12	ZHENG Z , LEI T , WANG J , et al. Catalytic cracking of soybean oil for biofuel over γ-Al₂O₃/CaO composite catalyst[J]. Journal of the Brazilian Chemical Society, 2019, 30 (2): 359- 370.
13	YIGEZU Z D , MUTHUKUMAR K . Biofuel production by catalytic cracking of sunflower oil using vanadium pentoxide[J]. Journal of Analytical & Applied Pyrolysis, 2015, 112, 341- 347.
14	SUGAMI Y , MINAMI E , SAKA S . Hydrocarbon production from coconut oil by hydrolysis coupled with hydrogenation and subsequent decarboxylation[J]. Fuel, 2017, 197, 272- 276. doi: 10.1016/j.fuel.2017.02.038
15	LU X P , GU F N , LIU Q , et al. VO_x promoted Nicatalysts supported on the modified bentonite for CO and CO₂ methanation[J]. Fuel Processing Technology, 2015, 135, 34- 46. doi: 10.1016/j.fuproc.2014.10.009
16	ROKICIN'SKA S , NATKAN'SKI P , DUDEK B , et al. Co₃O₄-pillared montmorillonite catalysts synthesized by hydrogel-assisted route for total oxidation of toluene[J]. Applied Catalysis B: Environmental, 2016, 195, 59- 68. doi: 10.1016/j.apcatb.2016.05.008
17	高龙超. 催化裂解油脂制备液体燃料油的研究[D]. 杭州: 浙江工业大学, 2013.

	C7	C8	C9	C10	C11	C12	C13	C14	C15
液相liquid phase	0.00	0.00	2.51	13.88	15.67	40.98	12.47	10.98	3.50
气相gas phase	7.00	9.00	11.89	16.19	10.95	22.80	14.01	2.56	5.60

油种类 oil type	运动黏度(20 ℃)/(mm²·s^-1) kinematic viscosity	密度/(g·cm^-3) density	含氧量/% oxygen content	低位热值/(kJ·kg^-1) low calorific value	酸值/(mg·g^-1) acid value
椰子油coconut oil	58.30	0.915	15.1	35400	0.9
液相裂解液LPC liquid	4.03	0.853	10.0	38100	118.8
气相催化裂解液GPCC liquid	4.11	0.846	6.9	39800	2.8
生物柴油biodiesel	4.52	0.881	11.1	37400	0.5
0#柴油0# diesel	3.67	0.834	0	42600	0

[1]	舒恒毅, 郑志锋, 李水荣, 刘守庆, 何宏舟, 黄元波. 油酸甲酯烯烃复分解合成1-癸烯的工艺优化[J]. 生物质化学工程, 2021, 55(5): 8-14.
[2]	赵红叶, 邬怡, 杜政江, 刘全生, 周华从. 钴-桔皮炭氢转移催化剂的制备及其催化加氢性能研究[J]. 生物质化学工程, 2021, 55(4): 14-20.
[3]	刘志超, 王妍艳, 郑方栋, 万迪. 基于Py-GC/MS的玉米秸秆快速热解实验研究[J]. 生物质化学工程, 2021, 55(4): 29-33.
[4]	王晓璐, 姚雪峰, 陈宇新, 周华从, 刘全生. 锆/铪基催化剂催化转移加氢反应的研究进展[J]. 生物质化学工程, 2021, 55(4): 66-76.
[5]	李睿帆, 陈玉保, 赵永彦, 庄诗韵, 张文杰. Pd-Al₂O₃-BEA催化麻疯树油制航空煤油的工艺优化[J]. 生物质化学工程, 2021, 55(3): 55-61.
[6]	张洁, 段荣帅, 李子江, 王慧, 张宁, 张淑亚, 司传领. 生物质基碳气凝胶的研究进展[J]. 生物质化学工程, 2021, 55(1): 91-100.
[7]	尚双, 兰奎, 王艳, 张娟娟, 秦振华, 李建芬. 生物质焦油重整催化剂的研究进展[J]. 生物质化学工程, 2020, 54(6): 65-73.
[8]	阚玉娜, 陈冰炜, 翟胜丞, 潘明珠, 梅长彤. 有机溶剂自催化和协同预处理促进木质纤维原料酶解研究进展[J]. 生物质化学工程, 2020, 54(6): 74-82.
[9]	彭昭霞,李艳红,陈亿琴,梁光兵,黄勇,訾昌毓. 生物质灰硅资源高附加值利用的研究进展[J]. 生物质化学工程, 2020, 54(2): 61-66.
[10]	尹航,徐卫,孙云娟,许玉,应浩,宁思云. 生物质合成气催化甲烷化技术研究进展[J]. 生物质化学工程, 2019, 53(5): 49-56.
[11]	王学涛,苏晓昕. 助剂对镍基生物质焦油重整催化剂性能影响的研究进展[J]. 生物质化学工程, 2019, 53(2): 61-66.
[12]	亚力昆江·吐尔逊, 别尔德汗·瓦提汗, 迪丽努尔·塔力甫, 阿布力克木·阿布力孜, 徐绍平. 生物质和煤共热解特性及催化剂对热解的影响[J]. 生物质化学工程, 2018, 52(5): 31-36.
[13]	郑玉龙, 李淑颖, 庞帝琼, 杨富裕. 微生物预处理能源草转化生物能源的研究进展[J]. 生物质化学工程, 2018, 52(2): 51-58.
[14]	杨艳平, 罗云龙, 沈明贵, 商士斌, 宋湛谦. 磁性颗粒负载磺酸功能化离子液体催化纤维素水解的研究[J]. 生物质化学工程, 2017, 51(6): 6-10.
[15]	徐海升, 王豪, 王博. 生物燃料加氢脱氧催化剂研究进展[J]. 生物质化学工程, 2017, 51(6): 55-61.