Catalytic conversion of palm oil to aromatics on Zn/HZSM-5 zeolites

doi:10.11949/0438-1157.20190424

Abstract

Abstract:

HZSM-5 zeolite can be used in the process of catalytic conversion of fatty acid esters to produce aromatic hydrocarbons and low-carbon olefins. However, the yield of aromatics over untreated HZSM-5 zeolite is low. Modification of HZSM-5 zeolite with transition metal can optimize the acidity and greatly increase the yield of aromatics. A series of Zn/HZSM-5 zeolites with different zinc content were prepared by equal volume impregnation, and the modified zeolites were characterized by XRD, XRF, XPS, NH₃-TPD, SEM, TEM, Py-IR, and N₂physical adsorption-desorption. The results showed that the crystal structure of Zn/HZSM-5 was not changed, and the zinc was uniformly distributed on the surface and pores of HZSM-5 zeolites. Catalytic conversion of palm oil on Zn/HZSM-5 zeolite with Zn content of 3% (mass) showed the best catalytic performance. The content of aromatics in the obtained liquid hydrocarbons was as high as 87.92% (mass), and the yield of aromatics reached 59.44% (mass).

Key words: HZSM-5, Zn modification, palm oil, catalytic conversion, aromatic hydrocarbon

摘要：

HZSM-5分子筛可用于脂肪酸酯催化转化生产芳烃、低碳烯烃等过程。未经过处理的HZSM-5分子筛芳烃产率较低，使用过渡金属改性后的HZSM-5分子筛酸性质发生了改变，能够提高芳烃的收率。以等体积浸渍法对HZSM-5分子筛进行改性，制备了不同锌含量的 Zn/HZSM-5分子筛，并进行了 XRD、XRF、XPS、NH₃-TPD、SEM、TEM、Py-IR、N₂物理吸附-脱附等多种表征，结果表明锌的引入没有改变 HZSM-5的晶体结构，锌物种能均匀分布在 HZSM-5分子筛表面及孔道。棕榈油催化转化实验结果显示Zn含量（质量分数）为3% 的 Zn/HZSM-5有最好的催化效果，芳烃在液相烃类所占比例（质量分数）为87.92%，芳烃收率（质量分数）为59.44%。

关键词: HZSM-5, Zn改性, 棕榈油, 催化转化, 芳烃

CLC Number:

TE 624

Zhiyuan AN, Chao ZHU, Yibin LIU, Xiang FENG, Xin JIN, Xiaobo CHEN, Chaohe YANG. Catalytic conversion of palm oil to aromatics on Zn/HZSM-5 zeolites[J]. CIESC Journal, 2019, 70(11): 4289-4297.

安志远, 朱超, 刘熠斌, 冯翔, 金鑫, 陈小博, 杨朝合. Zn/HZSM-5分子筛催化棕榈油多产芳烃的研究[J]. 化工学报, 2019, 70(11): 4289-4297.

Figures/Tables 14

References 44

1	刘全杰, 方向晨, 徐会青, 等 . 含分子筛重整催化剂的反应性能研究[J]. 工业催化, 2009, 17(12): 37-40.
	Liu Q J , Fang X C , Xu H Q , al et .Study on catalytic properties of reforming catalysts containing zeolite[J]. Industrial Catalysis, 2009, 17(12): 37-40.
2	孔德金, 杨为民 . 芳烃生产技术进展[J]. 化工进展, 2011, 30(1): 16-25.
	Kong D J , Yang W M . Advance in technology for production of aromatic hydrocarbons[J]. Chemical Industry and Engineering Progress, 2011, 30(1): 16-25.
3	李燕秋, 白尔铮, 段启伟 . 芳烃生产技术的新进展[J]. 石油化工, 2005, 34(4): 309-315.
	Li Y Q , Bai E Z , Duan Q W . Recent progress of aromatics production technologies[J]. Petrochemical Technology, 2005, 34(4): 309-315.
4	童浩 . 离子液体萃取分离芳烃/脂肪烃的研究[D]. 北京: 中国石油大学 (北京), 2016.
	Tong H . Separation of aromatic and aliphatic hydrocarborn by ionic liquids[D]. Beijing: China University of Petroleum, 2016.
5	张岚, 吴平 . 能源结构低碳转型路线图[J]. 高科技与产业化, 2010, 6(9): 49-51.
	Zhang L , Wu P . Low-carbon energy structure transformation roadmap[J]. High-Technology & Industrialization, 2010, 6(9): 49-51.
6	夏亚穆, 焦斌 . 非均相催化法生产生物柴油的研究进展[J]. 化学与生物工程, 2012, 29(3): 6-8.
	Xia Y M , Jiao B . Research progress of biodiesel production by heterogeneous catalysis[J]. Chemistry & Bioengineering, 2012, 29(3): 6-8.
7	Kokotailo G T , Lawton S L , Olson D H . Structure of synthetic zeolite ZSM-5[J]. Nature, 1978, 272(5652): 437-438.
8	蔡文静, 闫昊, 冯翔, 等 . 不同碳链长度脂肪酸甲酯的催化裂化产物分布规律[J]. 化工学报, 2016, 68(5): 2057-2065.
	Cai W J , Yan H , Feng X , et al . Product distribution in catalytic cracking of fatty acid methyl esters with different carbon chain lengths[J]. CIESC Journal, 2016, 68(5): 2057-2065.
9	Kim Y H , Lee K H , Nam C M , et al . Formation of hierarchical pore structures in Zn/ZSM‐5 to improve the catalyst stability in the aromatization of branched olefins[J]. ChemCatChem, 2012, 4(8): 1143-1153.
10	Prasad Y S , Bakhshi N N , Mathews J F , et al . Catalytic conversion of canola oil to fuels and chemical feedstocks(Ⅱ): Effect of co‐feeding steam on the performance of HZSM‐5 catalyst[J]. The Canadian Journal of Chemical Engineering, 1986, 64(2): 285-292.
11	Ngo T A , Kim J , Kim S K , et al . Pyrolysis of soybean oil with H-ZSM5 (Proton-exchange of Zeolite Socony Mobil# 5) and MCM41 (Mobil Composition of Matter No. 41) catalysts in a fixed-bed reactor[J]. Energy, 2010, 35(6): 2723-2728.
12	Twaiq F A , Zabidi N A M , Bhatia S . Catalytic conversion of palm oil to hydrocarbons: performance of various zeolite catalysts[J]. Industrial & Engineering Chemistry Research, 1999, 38(9): 3230-3237.
13	Hilten R , Speir R , Kastner J , et al . Production of aromatic green gasoline additives via catalytic pyrolysis of acidulated peanut oil soap stock[J]. Bioresource Technology, 2011, 102(17): 8288-8294.
14	Botas J A , Serrano D P , García A , et al . Catalytic conversion of rapeseed oil into raw chemicals and fuels over Ni- and Mo-modified nanocrystalline ZSM-5 zeolite[J]. Catalysis Today, 2012, 195(1): 59-70.
15	Bayat A . Enhanced performance of methyl ester to renewable aromatics via thermocatalytic conversion over metal‐modified HZSM‐5 zeolites: an experimental study[J]. ChemistrySelect, 2018, 3(47): 13338-13344.
16	Zhao X , Wei L , Cheng S , et al . Catalytic cracking of camelina oil for hydrocarbon biofuel over ZSM-5-Zn catalyst[J]. Fuel Processing Technology, 2015, 139: 117-126
17	Ramos R , García A , Botas J A , et al . Enhanced production of aromatic hydrocarbons by rapeseed oil conversion over Ga and Zn modified ZSM-5 catalysts[J]. Industrial & Engineering Chemistry Research, 2016, 55(50): 12723-12732.
18	Danuthai T , Jongpatiwut S , Rirksomboon T , et al . Conversion of methylesters to hydrocarbons over Zn-modified H-ZSM-5 zeolite catalyst[J]. Catalysis Letters, 2009, 132(1/2): 197-204.
19	Roshanaei A , Alavi S M . Using two-zone fluidized bed reactor in propane aromatization over Zn/HZSM-5 catalyst[J]. Fuel Processing Technology, 2018, 176: 197-204.
20	Pinilla-Herrero I , Borfecchia E , Holzinger J , et al . High Zn/Al ratios enhance dehydrogenation vs hydrogen transfer reactions of Zn-ZSM-5 catalytic systems in methanol conversion to aromatics[J]. Journal of Catalysis, 2018, 362: 146-163.
21	He P , Wang A , Meng S , et al . Impact of Al sites on the methane co-aromatization with alkanes over Zn/HZSM-5[J]. Catalysis Today, 2019, 323: 94-104.
22	Wei Z , Chen L , Cao Q , et al . Steamed Zn/ZSM-5 catalysts for improved methanol aromatization with high stability[J]. Fuel Processing Technology, 2017, 162: 66-77.
23	Ramya G , Sudhakar R , Joice J A I , et al . Liquid hydrocarbon fuels from jatropha oil through catalytic cracking technology using AlMCM-41/ZSM-5 composite catalysts[J]. Applied Catalysis A: General, 2012, 433: 170-178.
24	Taufiqurrahmi N , Bhatia S . Catalytic cracking of edible and non-edible oils for the production of biofuels[J]. Energy & Environmental Science, 2011, 4(4): 1087-1112.
25	Rahimi N , Karimzadeh R . Catalytic cracking of hydrocarbons over modified ZSM-5 zeolites to produce light olefins: a review[J]. Applied Catalysis A: General, 2011, 398(1/2): 1-17.
26	Choudhary V R , Jana S K . Benzylation of benzene by benzyl chloride over Fe-, Zn-, Ga- and In-modified ZSM-5 type zeolite catalysts[J]. Applied Catalysis A: General, 2002, 224(1/2): 51-62.
27	Chen L , Li H , Fu J , et al . Catalytic hydroprocessing of fatty acid methyl esters to renewable alkane fuels over Ni/HZSM-5 catalyst[J]. Catalysis Today, 2016, 259: 266-276.
28	Sang S , Chang F , Liu Z , et al . Difference of ZSM-5 zeolites synthesized with various templates[J]. Catalysis Today, 2004, 93: 729-734.
29	龙化云 . 全馏分FCC汽油改质芳构化催化剂研究[D]. 大连: 大连理工大学, 2012.
	Long H Y . Study on the aromatization catalyst for full-range FCC gasoline upgrading[D]. Dalian: Dalian University of Technology, 2012.
30	Chen X , Dong M , Niu X , et al . Influence of Zn species in HZSM-5 on ethylene aromatization[J]. Chinese Journal of Catalysis, 2015, 36(6): 880-888.
31	Berndt H , Lietz G , Völter J . Zinc promoted H-ZSM-5 catalysts for conversion of propane to aromatics(Ⅱ): Nature of the active sites and their activation[J]. Applied Catalysis A: General, 1996, 146(2): 365-379.
32	Triwahyono S , Jalil A A , Mukti R R , et al . Hydrogen spillover behavior of Zn/HZSM-5 showing catalytically active protonic acid sites in the isomerization of n-pentane[J]. Applied Catalysis A General, 2011, 407(1): 91-99.
33	Su X , Zan W , Bai X , et al . Synthesis of microscale and nanoscale ZSM-5 zeolites: effect of particle size and acidity of Zn modified ZSM-5 zeolites on aromatization performance[J]. Catalysis Science & Technology, 2017, 7(9): 1943-1952.
34	Cao R , Zhao H , Cheng M J , et al . Synergistic mechanism of aromatization of ethane and ethene over Zn/HZSM-5 zeolite[J]. Chemical Research in Chinese Universities, 1996, 17(1): 102-106.
35	辛勤, 罗孟飞 . 现代催化研究方法[M]. 北京: 科学出版社, 2009: 21.
	Xin Q , Luo M F . Modern Catalytic Research Method[M]. Beijing: Science Press, 2009: 21.
36	Yang C , Qiu M , Hu S , et al . Stable and efficient aromatic yield from methanol over alkali treated hierarchical Zn-containing HZSM-5 zeolites[J]. Microporous and Mesoporous Materials, 2016, 231: 110-116.
37	Wang F , Xiao W , Gao L , et al . The growth mode of ZnO on HZSM-5 substrates by atomic layer deposition and its catalytic property in the synthesis of aromatics from methanol[J]. Catalysis Science & Technology, 2016, 6(9): 3074-3086.
38	Lin B , Wang J , Huang Q , et al . Aromatic recovery from distillate oil of oily sludge through catalytic pyrolysis over Zn modified HZSM-5 zeolites[J]. Journal of Analytical and Applied Pyrolysis, 2017, 128: 291-303.
39	何学良, 詹永厚, 李疏松 . 内燃机燃料[M]. 北京: 中国石化出版社, 1999: 395-430.
	He X L , Zhan Y H , Li S S . Automotive Fuels[M]. Beijing: China Petrochemical Press, 1999: 395-430.
40	田华, 李春义, 杨朝合, 等 . 棕榈油的催化转化研究[J]. 石油学报 (石油加工), 2008, 24(3): 256-262.
	Tian H , Li C Y , Yang C H , et al . Study on catalytic conversion of palm oil[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2008, 24(3): 256-262.
41	Chen N Y . Shape Selective Catalysis in Industrial Applications[M]. Florida: Chemical Rubber Company Press, 1996: 30-31
42	Li Y , Liu S , Xie S , et al . Promoted metal utilization capacity of alkali-treated zeolite: preparation of Zn/ZSM-5 and its application in 1-hexene aromatization[J]. Applied Catalysis A: General, 2009, 360(1): 8-16.
43	Idem R O , Katikaneni S P R , Bakhshi N N . Catalytic conversion of canola oil to fuels and chemicals: roles of catalyst acidity, basicity and shape selectivity on product distribution[J]. Fuel Processing Technology, 1997, 51(1/2): 101-125.
44	Zhang C , Kwak G , Park H G , et al . Light hydrocarbons to BTEX aromatics over hierarchical HZSM-5: effects of alkali treatment on catalytic performance[J]. Microporous and Mesoporous Materials, 2019, 276: 292-301.

性质	数值
密度(25℃)/(g·cm^-3)	0.88
黏度(40℃)/(mPa·s)	35.41
元素组成（质量分数）/%
C	75.65
H	12.28
O(减差法计算)	15.07
N	<0.1
S	<0.1
主要脂肪酸（质量分数）/%
油酸（C_18:1）	38.8
亚油酸（C_18:2）	10.1
棕榈酸（C_16:0）	43.5
硬脂酸（C_18:0）	4.2

性质	数值
密度(25℃)/(g·cm^-3)	0.88
黏度(40℃)/(mPa·s)	35.41
元素组成（质量分数）/%
C	75.65
H	12.28
O(减差法计算)	15.07
N	<0.1
S	<0.1
主要脂肪酸（质量分数）/%
油酸（C_18:1）	38.8
亚油酸（C_18:2）	10.1
棕榈酸（C_16:0）	43.5
硬脂酸（C_18:0）	4.2

分子筛	酸量/( mmol·g^-1)					Strong/Weak	L/B
分子筛	Total	Strong	Weak	B	L	Strong/Weak	L/B
1-Z5	1.25	0.64	0.61	0.87	0.38	1.05	0.44
2-Z5	1.06	0.47	0.59	0.45	0.61	0.8	1.34
3-Z5	1.01	0.33	0.68	0.29	0.72	0.48	2.52
4-Z5	0.95	0.18	0.77	0.15	0.80	0.24	5.3

分子筛	酸量/( mmol·g^-1)					Strong/Weak	L/B
分子筛	Total	Strong	Weak	B	L	Strong/Weak	L/B
1-Z5	1.25	0.64	0.61	0.87	0.38	1.05	0.44
2-Z5	1.06	0.47	0.59	0.45	0.61	0.8	1.34
3-Z5	1.01	0.33	0.68	0.29	0.72	0.48	2.52
4-Z5	0.95	0.18	0.77	0.15	0.80	0.24	5.3

催化剂	A _BET/ (m²·g^-1)	A _micro/ (m²·g^-1)	V _total/ (cm³·g^-1)	V _micro/ (cm³·g^-1)	d _aver/nm
1-Z5	396	385	0.18	0.16	1.85
2-Z5	385	372	0.18	0.16	1.87
3-Z5	368	353	0.17	0.15	1.90
4-Z5	342	325	0.16	0.14	1.89