Production of fuel oil from agricultural residues by hydropyrolysis integrated with volatile catalytic hydrogenation

Agricultural residue is an important biomass resource in China. Utilization of agricultural residue for production of high-quality fuel oil is an attractive and challenging topic towards the goals of “Carbon Peaking and Carbon Neutrality”. Biomass hydropyrolysis integrated with volatile catalytic hydrogenation is a new process that can efficiently improve the yield and quality of bio-oil. This work is purposed to explore this new biomass conversion technology by laboratory experiments using a tandem pressurized fixed bed reactor. A bimetallic molecular sieve catalyst (NiMo-HZSM-5) was prepared by an impregnation method and used for catalytic hydrogenation. Biomass was hydropyrolyzed under a condition of 5 MPa H₂ pressure, 15℃/min heating rate and 700℃ final temperature to generate volatile matter, which was online hydrogenated through the NiMo-HZSM-5 catalyst bed under a condition of 5 MPa H₂ pressure, 320℃ reaction temperature and 26 s residence time (corresponding to space velocity of 112.5 h⁻¹). The paper firstly presents the oil production results of three types of agricultural residue, corn stalk, cotton stalk and peanut straw by the catalytic hydrogenetion. The paper is then devoted to further clarifying the conversion characteristics of different biomass fiber constituents by means of the water washing and acid washing pretreatments of three agricultural residues as well as by adopting cellulose and lignin as model compounds. Results showed that in the case of non-catalytic hydrogenation, all of the bio-oils obtained from three agricultural residues contained oxygenates and aromatic hydrocarbons as two main classes of compounds, and that from peanut straw also contained a high proportion of nitrogenous compounds. In contrast, all of the bio-oils derived from three agricultural residues by the catalytic hydrogenation (CH bio-oils) contained almost neither oxygenates nor nitrogenous compounds. The yields of CH bio-oils reached 10.3%–15.9% for three agricultural residues. The CH-bio-oils were composed of 73.0–84.8% saturated aliphatic hydrocarbons (mainly cyclopentanes, cyclohexanes, and perhydro- naphthalenes), 6.1%–13.1% partially hydrogenated aromatic hydrocarbons (mainly di-, tetra-hydronaphthalenes) and a small amount of monocyclic aromatic hydrocarbons. The result highlights that the two-stage process of hydrogenation pyrolysis integrated with NiMo-HZSM-5 catalytic hydrogenation can effectively convert agricultural residue into a kind of high-quality bio-oil composed mainly of alicyclic hydrocarbons. The water washing could remove about half of neutral extractives from each of three agricultural resides. After the water washing, three agricultural residues showed increases in the yields of CH bio-oil to 18.1%–18.5%, suggesting that neutral extractives are less conducive to the production of CH bio-oil compared to other fiber components. The acid washing enabled cellulose and lignin to be left in the agricultural residues as main components. Via this pretreatment, the yields of CH bio-oil increased to 18.2%–22.5% for three agricultural residues, with cotton stalk having the highest yield. The yields of typical aliphatic hydrocarbon compounds (methyl-cyclopentane, methyl-cyclohexane and decahydro-naphthalene) from all three agricultural residues were increased by the acid washing. The study using model compounds revealed that cellulose is a fiber for not only achieving a high yield of CH bio-oil but also selectively producing aliphatic hydrocarbon compounds such as cyclopentane, cyclohexane, and decahydro-naphthalene. Meanwhile, lignin has a lower yield of bio-oil, and it tends to produce monocyclic aromatic hydrocarbons. Lignin can also generate cyclohexane compounds and partially hydrogenated polycyclic aromatic hydrocarbons, but it has a low propensity to the formation of cyclopentane compounds. This study has provided a new technical route to utilizing agricultural residues for high-efficient production of fuel oil.