Pd-β/MCM-41复合分子筛加氢裂解废食用油性能研究

doi:10.3969/j.issn.1673-5854.2019.01.002

生物质化学工程 ›› 2019, Vol. 53 ›› Issue (1): 8-16.doi: 10.3969/j.issn.1673-5854.2019.01.002

Pd-β/MCM-41复合分子筛加氢裂解废食用油性能研究

赵倩^1,²,闻源振^1,³,靳海波^1,²,何广湘^1,^2,*()

1. 北京石油化工学院化学工程学院, 北京 102617
2. 燃料清洁化及高效催化减排技术北京市重点实验室, 北京 102617
3. 中国石油大学(北京) 化学工程学院，北京 102249

收稿日期:2017-11-29 出版日期:2019-01-30 发布日期:2019-03-15
通讯作者: 何广湘 E-mail:hgx@bipt.edu.cn
作者简介:赵倩(1991—),女,河南商丘人,硕士,研究方向为清洁能源转化与利用
基金资助:
国家自然科学基金资助项目(91634101);北京市属高校高水平教师队伍建设支持计划高水平创新团队建设计划项目(IDHT20180508)

Pd-β/MCM-41 Composite Molecular Sieve in Hydrocracking Waste Cooking Oil Reaction

Qian ZHAO^1,²,Yuanzhen WEN^1,³,Haibo JIN^1,²,Guangxiang HE^1,^2,*()

1. College of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
2. Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology, Beijing 102617, China
3. College of Chemical Engineering, China University of Petroleum, Beijing 102249, China

Received:2017-11-29 Online:2019-01-30 Published:2019-03-15
Contact: Guangxiang HE E-mail:hgx@bipt.edu.cn
Supported by:
国家自然科学基金资助项目(91634101);北京市属高校高水平教师队伍建设支持计划高水平创新团队建设计划项目(IDHT20180508)

摘要/Abstract

摘要：

以碱处理β沸石作为硅铝源，以CTAB为模板剂，合成了β/MCM-41介孔-微孔复合分子筛，以其为载体制备Pd-β/MCM-41复合分子筛催化剂，利用XRD、N₂吸附-脱附、NH₃-TPD和XRF等技术对其进行了表征，并与γ-Al₂O₃、USY、ZSM-5等载体制备的催化剂比较了废食用油加氢裂解活性。结果表明：β/MCM-41复合分子筛同时具备β沸石和MCM-41分子筛的结构，β/MCM-41为载体时，Pd-β/MCM-41催化剂具有适宜的中强酸性中心，适宜的孔道分布结构，催化剂加氢裂解废食用油的活性最高。此外还考察了催化剂制备条件对废食用油加氢裂解反应的影响，结果表明：采用离子交换法制备负载量2%的Pd-β/MCM-41复合分子筛催化剂、焙烧温度为500 ℃时，催化剂对废食用油加氢裂解的效果最好。此时，原料油的转化率可以达到85.9%，生物汽油的收率可以达到16.4%，生物柴油的收率达到17.8%，且此催化剂水热稳定性较好，再生性能良好，工业化应用前景较好。

关键词: β/MCM-41介孔-微孔复合分子筛, 钯, 废食用油, 加氢裂解

Abstract:

β/MCM-41 meso-microporous composite molecular sieves were synthesized with β zeolite as silica-alumina source and CTAB as template. And then Pd-β/MCM-41 catalyst was prepared. The catalyst was characterized by XRD, N₂ adsorption-desorption, NH₃-TPD and XRF. And the catalytic hydrocracking activity of Pd-β/MCM-41 was separately investigated and compared with that of Pd catalysts which were prepared with γ-Al₂O₃, USY and ZSM-5 as carriers. The study showed that β/MCM-41 composite molecular sieves had both the structures of β zeolite and MCM-41 molecular sieve. Pd-β/MCM-41 catalyst had suitable medium-strong acidity center and suitable pore distribution structure and it had the highest activity of the hydrocracking. Meanwhile, the influence of the catalyst synthesis conditions on the catalyst activity was discussed. The results showed that the best hydrocracking activity on the vegetable oil was acquired as preparation 2% Pd on β/MCM-41 composite molecular sieves by ion exchange and the calcination temperature of 500 ℃. The conversion rate of raw oil reached 85.9%, and the yield of biogasoline could reach 16.4%, and the yield of biodiesel reached 17.8%. The composite molecular sieve catalyst had better thermal stability, regeneration property and prospect for industrial application.

Key words: β/MCM-41 meso-microporous composite molecular sieve catalyst, Pd, waste cooking oil, hydrocracking

中图分类号:

赵倩,闻源振,靳海波,何广湘. Pd-β/MCM-41复合分子筛加氢裂解废食用油性能研究[J]. 生物质化学工程, 2019, 53(1): 8-16.

Qian ZHAO,Yuanzhen WEN,Haibo JIN,Guangxiang HE. Pd-β/MCM-41 Composite Molecular Sieve in Hydrocracking Waste Cooking Oil Reaction[J]. Biomass Chemical Engineering, 2019, 53(1): 8-16.

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样品 samples	制备方法 preparation methods	BET比表面积/(m²·g^-1) BET specific surface area	孔容/(cm³·g^-1) pore volume
β/MCM-41	碱溶法base-dissolving method	634.4	0.6476
β+MCM-41	机械混合mechanical mixing	530.8	0.5747

制备方法 prepaiation methods	不同组分负载量different component loading/%
制备方法 prepaiation methods	NaO	Al₂O₃	SiO₂	SO₃	CaO	TiO₂	Fe₂O₃	NiO	Cl	Pd
离子交换法ion exchange method	0.350	6.40	91.0	0.0602	0.0569	0.0513	0.237	0.0510	—	1.39
浸渍法负载impregnation method	0.119	6.58	90.3	0.1150	0.0571	—	0.413	—	—	1.87

种类 type	不同成分的质量分数mass fraction of different ingredients/%
种类 type	链烷烃 alkane	环烷烃 cycloalkane	不饱和烃 unsaturated hydrocarbon	其他含氧化合物 other oxygenates
生物汽油biogasoline(C5~C11)/%	33.95	49.03	13.37	3.65
生物柴油biodiesel(C12~C18)/%	21.78	10.45	38.43	29.30

温度/℃ temperature	转化率/% conversion rate	生物汽油/% biogasoline		生物柴油/% biodiesel		焦炭/% coke		气体/% gas
温度/℃ temperature	转化率/% conversion rate	收率 yield	选择性 selective	收率 yield	选择性 selective	收率 yield	选择性 selective	收率 yield	选择性 selective
390	43.13	4.29	9.95	10.66	24.85	0.69	1.61	27.42	63.59
420	55.46	4.91	8.85	15.02	27.09	1.66	3.00	33.87	61.06
450	83.63	14.84	17.75	16.73	20.00	2.33	2.79	49.72	59.45
480	85.85	15.64	18.22	16.97	19.77	2.55	2.97	50.69	59.04
510	89.99	12.37	13.74	14.06	15.62	3.69	4.10	59.87	66.53

催化剂 catalytic	转化率/% conversion rate	汽油收率/% biogasoline yield	柴油收率/% biodiesel yield	汽油选择性/% biogasoline selective	柴油选择性/% biodiesel selective
Pd-γ-Al₂O₃	58.6	3.7	10.3	6.3	17.5
Pd-USY	65.1	10.6	14.6	16.3	22.5
Pd-ZSM-5	76.2	13.5	15.0	17.7	19.7
Pd-β/MCM-41	80.9	15.6	16.4	19.3	20.3

Pd-β/MCM-41复合分子筛加氢裂解废食用油性能研究

Pd-β/MCM-41 Composite Molecular Sieve in Hydrocracking Waste Cooking Oil Reaction

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负载方式 loading methods	转化率/% conversion rate	汽油收率/% biogasoline yield	柴油收率/% biodiesel yield	汽油选择性/% biogasoline selective	柴油选择性/% biodiesel selective
离子交换法 ion exchange method	80.9	15.6	16.4	19.3	20.3
浸渍法 impregnation method	80.3	11.2	13.3	13.9	16.6

催化剂 catalyst	转化率/% conversion rate	汽油收率/% biogasoline yield	柴油收率/% biodiesel yield	汽油选择性/% biogasoline selectivity	柴油选择性/% biodiesel selectivity
水热前before water vapor	81.7	16.6	17.4	20.3	21.2
水热后after water vapor	81.1	15.9	17.0	19.5	20.9

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