Study on Oil⁃Soluble Molybdenum Sulfide Catalyzed Hydrodeoxygenation of Waste Cooking Oil in a Suspended⁃Bed Reactor

doi:10.12422/j.issn.1006-396X.2026.02.003

Abstract

Abstract:

An oil⁃soluble molybdenum sulfide catalyst (MS⁃1) was prepared by a ‘one⁃pot’ synthesis method and characterized using XRD,FT⁃IR,XPS,and HR⁃TEM.The hydrodeoxygenation (HDO) performance toward methyl oleate and the hydrotreating capability for waste oils (with phosphorus,chlorine,and total metal contents of 18.14,138.80,and 173.60 µg/g,respectively) were evaluated in a high⁃pressure reactor.The results indicate that two⁃dimensional monolayer MoS2 active species were generated in situ during reaction,and the synthesized catalyst exhibited excellent overall performance.Under the conditions of a catalyst dosage of 380 µg/g,a reaction temperature of 360 °C,an initial H2 pressure of 4.0 MPa,and a reaction time of 3.0 h,the deoxygenation rates of methyl oleate and waste cooking oil reached 99.2% and 99.7%,respectively.The acid value and bromine value of the waste oil were significantly reduced from 173.60 mgKOH/g and 117.70 gBr/(100 g) to 5.28 mgKOH/g and 5.65 gBr/(100 g).The removal efficiencies of phosphorus,chlorine, and total metals were 92.17%,93.87%,and 96.92%,respectively.

Key words: Sulfidation state, Oil?soluble catalyst, Slurry bed, Waste cooking oil, Hydrodeoxygenation

摘要：

采用“一锅合成法”制备了油溶性硫化钼催化剂（MS⁃1），并通过XRD、FT⁃IR、XPS、HR⁃TEM等方法对MS⁃1催化剂进行了表征；以油酸甲酯和废弃油脂（地沟油，磷、氯和总金属的质量分数分别为18.14、138.80、173.60 µg/g）为原料，在高压釜中评价了该催化剂对油酸甲酯的加氢脱氧性能以及对废弃油脂的加氢净化能力。结果表明，催化剂在反应过程中原位生成了具有二维单层结构的MoS2活性中心；合成的催化剂表现出优异的综合性能；在催化剂质量分数为380 μg/g、反应温度为360 ℃、初始H2压力为4.0 MPa、反应时间为3.0 h的条件下，油酸甲酯和地沟油的脱氧率分别为99.2%和99.7%，其中地沟油的酸值、溴价分别由173.60 mgKOH/g、117.70 gBr/（100 g）大幅下降至5.28 mgKOH/g和5.65 gBr/（100 g）；磷、氯及总金属的脱除率分别达到92.17%、93.87%、96.92%。

关键词: 硫化态, 油溶性催化剂, 悬浮床, 地沟油, 加氢脱氧

CLC Number:

TQ519

Xinhao PAN, Zhaohao HAN, Beichen FU, Fengyu TIAN, Bin LIU, Yongming CHAI. Study on Oil⁃Soluble Molybdenum Sulfide Catalyzed Hydrodeoxygenation of Waste Cooking Oil in a Suspended⁃Bed Reactor[J]. Journal of Petrochemical Universities, 2026, 39(2): 21-30.

潘欣浩, 韩兆皓, 付北辰, 田丰宇, 刘宾, 柴永明. 油溶性硫化钼悬浮床催化废弃油脂加氢脱氧研究[J]. 石油化工高等学校学报, 2026, 39(2): 21-30.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.02.003

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I2/21

Figures/Tables 13

Fig.1 XRD spectra of MS?1 and MS

Fig.2 TG and DTG curves of MS?1

Table 1 ICP?OES detection and elemental analysis results of catalyst

检测元素	w/%
检测元素	MS⁃1	MS
^aC和^aH	74.62	1.45
^aN	1.36	<0.10
^aS	11.49	45.88
^bMo	10.52	48.67

Fig.3 MS?1 state in methyl oleate and waste cooking oil Ⅰ after dissolution and standing

Fig.4 Particle size distribution of MS in methyl oleate and waste cooking oil

Fig.5 FT?IR spectrum of MS?1

Fig.6 UV?vis spectra of MS?1 and MS

Fig.7 XPS spectra of MS?1 and MS

Fig.8 HR?TEM image of MS catalyst

Fig.9 The influence of different experimental conditions on the hydrodeoxygenation performance of methyl oleate

Fig.10 Photograph of waste cooking oil Ⅰ before and after hydrogenation purification

Fig.11 Yield and deoxygenation rate of hydrogenation products of waste cooking oil Ⅰ and Ⅱ

Table 2 Physicochemical properties of the feedstock and hydrodeoxygenation products

性质参数	检测结果
性质参数	反应前地沟油Ⅰ	反应前地沟油Ⅱ	反应后地沟油Ⅰ	反应后地沟油Ⅱ
颜色	棕褐色	棕褐色	澄清红褐色	澄清红褐色
20 ℃密度/（g·cm^-3）	0.925 3	0.917 7	0.831 0	0.858 3
总酸值/[mgKOH·g^-1]	173.60	91.30	5.28	3.20
凝点/℃	26.0	15.0	-10.0	-10.0
w（残炭）/%	1.13	0.36	<0.10	<0.10
w（硫）/（μg·g^-1）	3.35	3.70	1.43	1.29
w（氮）/（μg·g^-1）	5.37	6.09	2.17	2.47
w（氯）/（μg·g^-1）	138.80	31.20	8.50	3.10
w（总金属）/（μg·g^-1）	993.25	150.41	30.61	8.32
w（磷）/（μg·g^-1）	18.14	16.99	1.42	1.33
w（氧）/%	15.73	13.08	0.05	0.02
溴价/[gBr·（100 g）^-1]	117.77	44.34	5.65	2.38
脱氧率/%			99.71	99.82

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