Study on catalytic upgrading of pine sawdust pyrolysis oil by calcined ilmenite

XING Yingying; LI Yang; XU Shaoping; ZHANG Junwang; DU Lijun; XIAO Yahui

doi:10.12434/j.issn.2097-2547.20250170

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Study on catalytic upgrading of pine sawdust pyrolysis oil by calcined ilmenite

更新时间：2025-08-25

- Study on catalytic upgrading of pine sawdust pyrolysis oil by calcined ilmenite
- Vol. 50, Issue 8, Pages: 44-53(2025)
- 作者机构：
  
  1.大连理工大学化工学院，辽宁大连 116024
  2.河南大学能源科学与技术学院，河南郑州 450046
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250170
  CLC： TK6
- Received：09 April 2025，
  
  Revised：27 April 2025，
  
  Published：25 August 2025
- 稿件说明：
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邢莹莹,李扬,徐绍平等.煅烧钛铁矿催化松木屑热解油提质研究[J].低碳化学与化工,2025,50(8):44-53.

XING Yingying,LI Yang,XU Shaoping,et al.Study on catalytic upgrading of pine sawdust pyrolysis oil by calcined ilmenite[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(8):44-53.
邢莹莹,李扬,徐绍平等.煅烧钛铁矿催化松木屑热解油提质研究[J].低碳化学与化工,2025,50(8):44-53. DOI： 10.12434/j.issn.2097-2547.20250170.

XING Yingying,LI Yang,XU Shaoping,et al.Study on catalytic upgrading of pine sawdust pyrolysis oil by calcined ilmenite[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(8):44-53. DOI： 10.12434/j.issn.2097-2547.20250170.

摘要

针对生物质热解油氧含量大、品质差等问题，分别在落下床及其串联固定床反应装置中进行了松木屑快速热解和基于煅烧钛铁矿催化剂的生物质热解油提质研究，考察了热解温度、提质温度、催化剂质量与生物质进料速率比（

，g/(g·min

-1

)）及钛铁矿的不同煅烧温度对热解油产率和品质的影响。结果表明，热解温度550 °C时，热解油总产率及其轻质油产率均达到最大值。以600 °C煅烧的钛铁矿作为催化剂，在提质温度为550 °C、

为20 g/(g·min

-1

)条件下，热解

油品质显著提高，其中轻质油中烃类化合物相对含量由空白实验（采用石英砂床料）的11.1%增大至38.7%。提高钛铁矿的煅烧温度使得轻质油产率增大，热解油品质提高，但煅烧温度过高将导致轻质油产率显著减小，其中600 °C煅烧的钛铁矿具有最佳催化提质性能，其催化下的轻质油产率达到最大值（13.1%）且烃类化合物富集。结合XRD、N

吸/脱附、XPS和NH

-TPD等表征方法探究了煅烧钛铁矿物化性质变化与催化提质性能的构效关系。结果表明，600 °C煅烧的钛铁矿的比表面积最大，且其表面Fe

和晶格氧相对含量最大。Fe

在反应中会被部分还原并释放配位氧，形成大量氧空位。晶格氧和氧空位在热解油脱氧过程中分别作为氧供体和脱氧活性中心，通过氧化-还原循环实现高效脱氧。此外，升高煅烧温度还促进了钛铁矿表面强酸位点形成，进一步促进了热解油裂解和脱氧反应进行，但过多的强酸位点将引起热解油过度裂解，减小轻质油产率。

Abstract

In response to the problems of high oxygen content and poor quality of biomass pyrolysis oil

rapid pyrolysis of pine sawdust and the upgrading of the pyrolysis oil with calcined ilmenite as catalyst were studied in a free-fall reactor and it in tandem with a fixed-bed reactor respectively. The effects of pyrolysis temperatures

upgrading temperatures

catalyst mass to biomass feed rate ratios (

g/(g·min

-1

)) and different calcination temperatures of ilmenite on the pyrolysis oil yields and qualities were investigated. The results show that the total pyrolysis oil yield and light oil yield both reach their maximum values at the pyrolysis temperature of 550 ℃. With the ilmenite calcined at 600 ℃ as catalyst

under the upgrading temperature of 550 ℃ and

of 20 g/(g·min

-1

)

the pyrolysis oil quality is significantly improved. The relative hydrocarbon content in the light oil reaches to 38.7%

while that from the blank test (with quartz sand as bed material) is only 11.1%. Increasing the calcination temperatures of ilmenite allows for an increase of light oil yields and improvement of pyrolysis oil quality. However

the excessive calcination temperatures significantly reduce the light oil yields (13.1%). The ilmenite calcined at 600 ℃ exhibits the best catalytic upgrading performance

achieving maximum light oil yield and enrichment hydrocarbon compounds. Structure-performance relationships of structural changes and upgrading performances of calcin

ed ilmenite were investigated by XRD

adsorption/desorption

XPS and NH

-TPD. The results show that ilmenite calcined at 600 ℃ has the maximum specific surface area and the relative contents of surface Fe

and lattice oxygen. Fe

species are reduced in the reaction and release coordination oxygen

forming abundant oxygen vacancies. Lattice oxygen and oxygen vacancies separately act as oxygen donors and active sites in the deoxidation reaction of pyrolysis oil

achieving efficient deoxidation through the oxidation-reduction cycle. Additionally

increasing the calcination temperature also promotes the formation of strong acid sites on the surface of calcined ilmenite

further enhancing the cracking and deoxidation of pyrolysis oil. However

the excessive strong acid sites will lead to over-cracking of pyrolysis oil

reducing the light oil yields.

关键词

Keywords

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