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Production of phenolic compounds in Catalytic pyrolysis of bagasse lignin in the presence of Ca_(0.5)Pr_(0.5)FeO_(3)

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Journal of Rare Earths 2022年第2期40卷 279-288,I0004页

作者： Hongjing Han Qin Ge Mei Zhang Yanguang Chen Haiying Wang Yanan Zhang Yizhen Wang Hua Song Chunlei Zhang College of Chemistry&Chemical Engineering Northeast Petroleum UniversityDaqing 163318China Heilongjiang Provincial Key Laboratory of Oil&Cos Chemical Technology Daqing 163318China

Herein,sodium dodecylbenzene sulfonate(SDBS)was used as a template to control the synthesis of Ca_(0.5)Pr_(0.5)FeO_(3).Its microstructure,composition,and morphology were detected via X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FT-IR),and scanning electron microscopy(SEM).The properties of catalyzing bagasse lignin(BL)pyrolysis were determined by thermogravimetric analysis(TG)test and evaluation of a fixed bed alumina microreactor.The results show that the sample Ca_(0.5)Pr_(0.5)FeO_(3)regulated by SDBS has a cubic crystal phase,and the addition of SDBS does not cause phase transition.Moreover,when the SDBS concentration is 0.10 mol/L,the particle size is 200-500 nm and the specific surface area is 11.26 m^(2)/g.The yields of gas,liquid,and solid products in the BL Catalytic pyrolysis are 39.58 wt%,26.76 wt%and 32.36 wt%,respectively.The contents of CO_(2)and CO decrease from 54.07%and 4.98%to 45.29%and 3.23%,respectively.The liquid products are mainly guaiacol,syringol,and phenol,and the total selectivity of phenols is 83.67%,accompanied by a small amount of non-aromatic oxygen-containing compounds(five-membered ring(furan)or ester).Compared with the BL pyrolysis and Ca_(0.5)Pr_(0.5)FeO_(3)Catalytic pyrolysis products,the selectivity of guaiacol compounds increases by43.26%,while those of syringol compounds and phenylketones decrease by 30.08%and 3.39%,respectively.The selectivity of 2,6-dimethoxyphenol is 28.37%.After five Catalytic pyrolysis-regeneration cycles,the characteristic peaks of the catalyst do not change significantly and the particles are uniform,suggesting that the catalyst has good crystal phase stability and regeneration stability.

关键词： Bagasse lignin Calcium ferrite Pr doping Catalytic pyrolysis Guaiacol Rare earths

Reaction characteristics of maximizing light olefins and decreasing methane in C_(5) hydrocarbons Catalytic pyrolysis

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Petroleum Science 2023年第3期20卷 1909-1921页

作者： Mei-Jia Liu Gang Wang Shun-Nian Xu Tao-Ran Zheng Zhong-Dong Zhang Sheng-Bao He State Key Laboratory of Heavy Oil Processing China University of PetroleumBejing102249China Petrochemical Research Institute PetroChinaBejing102206China

When converting C_(5) hydrocarbons to light olefins by Catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilization efficiency,different generation pathways of light olefins and methane in the Catalytic pyrolysis of C_(5) hydrocarbons were analyzed,and the effects of reaction conditions and zeolite types were inves-tigated.Results showed that light olefins were mainly formed by breaking the C_(2)-C_(3) bond in the middle position,while methane was formed by breaking the C_(1)-C_(2) bond at the end.Meanwhile,it was discovered that the hydrogen transfer reaction could be reduced by about 90%by selecting MTT zeolite with 1D topology and FER zeolite with 2D topology under high weight hourly space velocity(WHSV)and high temperature operations,thus leading to the improvement of the light olefins selectivity for the Catalytic pyrolysis of n-pentane and 1-pentene to 55.12% and 74.60%,respectively.Moreover,the fraction ratio of terminal C_(1)-C_(2) bond cleavage was reduced,which would reduce the selectivity of methane to 6.63%and 1.83%.Therefore,zeolite with low hydrogen transfer activity and Catalytic pyrolysis process with high WHsV will be conducive to maximize light olefins and to decrease methane.

关键词： n-Pentane 1-Pentene Catalytic pyrolysis Light olefins Methane

Catalytic pyrolysis of Soybean Oil with CaO/Bio-Char Based Catalyst to Produce High Quality Biofuel

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Journal of Renewable Materials 2022年第12期10卷 3107-3118页

作者： Lujiang Xu Geliang Xie Xianjun Zhou Yucheng Liu Zhen Fang Biomass Group College of EngineeringNanjing Agricultural UniversityNanjing210031China

In this paper,CaO/bio-char was synthesized by directly co-pyrolysis of Ca(OH)_(2) and rice straw,and used as catalyst to Catalytic pyrolysis of soybean oil to produce high quality biofuel.In this co-pyrolysis process,CaO particles has been successfully embedded on the bio-char surface.During the Catalytic pyrolysis process,CaO/biochar showed a good catalytic performance on the deoxygenation of soybean oil.pyrolysis temperature affected the pyrolysis reactions and pyrolytic products distributions dramatically,higher pyrolysis temperature lead to seriously cracking reactions,lower bio-oil yield and higher gases yield,and lower pyrolysis temperature lead to higher bio-oil yield with higher oxygenated compounds content and lower hydrocarbons contents,the suitable pyrolysis temperature was around 650℃.Under the optimal conditions(650℃ with WHSV at 6.4 h^(−1) and carrier gas flow rate at 100 ml/min),the selectivity(%)of hydrocarbons in the bio-oil was more than 90%.CaO/bio-char catalyst still shows good catalytic deoxygenation activity after 4 cycles.1 g of CaO/bio-char catalyst can catalyze pyrolysis of 32 g of soybean oil to produce high-quality liquid fuel.Bio-char based catalyst has been proved to be a promising catalyst for catalytic conversion of triglyceride-based lipids into high quality liquid biofuel.

关键词： Carbonization CaO/bio-char Catalytic pyrolysis deoxygenation high quality biofuel

Thermodynamic analysis of reaction pathways and equilibrium yields for Catalytic pyrolysis of naphtha

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Frontiers of Chemical Science and Engineering 2022年第12期16卷 1700-1712页

作者： Dongyang Liu Yibo Zhi Yuen Bai Liang Zhao Jinsen Gao Chunming Xu State Key Laboratory of Heavy Oil Processing China University of Petroleum(Beijing)Beijing 102249China

The chain length and hydrocarbon type significantly affect the production of light olefins during the Catalytic pyrolysis of naphtha.Herein,for a better catalyst design and operation parameters optimization,the reaction pathways and equilibrium yields for the Catalytic pyrolysis of C_(5-8)n/iso/cyclo-paraffins were analyzed thermodynamically.The results revealed that the thermodynamically favorable reaction pathways for n/iso-paraffins and cyclo-paraffins were the protolytic and hydrogen transfer cracking pathways,respectively.However,the formation of light paraffin severely limits the maximum selectivity toward light olefins.The dehydrogenation cracking pathway of n/iso-paraffins and the protolytic cracking pathway of cyclo-paraffins demonstrated significantly improved selectivity for light olefins.The results are thus useful as a direction for future catalyst improvements,facilitating superior reaction pathways to enhance light olefins.In addition,the equilibrium yield of light olefins increased with increasing the chain length,and the introduction of cyclo-paraffin inhibits the formation of light olefins.High temperatures and low pressures favor the formation of ethylene,and moderate temperatures and low pressures favor the formation of propylene.n-Hexane and cyclohexane mixtures gave maximum ethylene and propylene yield of approximately 49.90%and 55.77%,respectively.This work provides theoretical guidance for the development of superior catalysts and the selection of proper operation parameters for the Catalytic pyrolysis of C_(5-8)n/iso/cyclo-paraffins from a thermodynamic point of view.

关键词： naphtha Catalytic pyrolysis reaction pathway equilibrium yield

Production of aryl oxygen-containing compounds by Catalytic pyrolysis of bagasse lignin over LaTi0.2Fe0.8O3 prepared by different methods

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Journal of Rare Earths 2020年第1期38卷 76-83页

作者： Haiying Wang Hongjing Han Enhao Sun Yanan Zhang Jinxin Li Yanguang Chen Hua Song Hongzhi Zhao Yue Kang College of Chemistry&Chemical Engineering Northeast Petroleum UniversityDaqing 163318China Provincial Key Laboratory of Oil&Gas Chemical Technology Daqing 163318China Daqing Petrochemical Research Center PetroChinaDaqing 163000China

To realize the resource and high-value utilization,a new approach,named bagasse lignin(BL) used to produce aryl oxygen-containing compounds by Catalytic pyrolysis over perovskite,was proposed,LaTi0.2Fe0.8O3(LTF) samples prepared by the sol-gel method(SG) and the solid-state reaction method(SS)were characterized.The catalytic action on BL pyrolysis was performed by the test of TG-DTG and the evaluation of the fixed bed micro-reactor,the components and contents of the products were determined.The results show that LTF samples have cubic perovskite phase,LTF prepared by SG(LTF-SG) is porous with larger specific surface area than LTF prepared by SS(LTF-SS).During the pyrolysis of BL,the addition of LTF lowers the pyrolysis temperature and the activation energy,the contents of CO2 and CO in gaseous products reduce by 4.6%-8.0% and 30.7%-34.3%,respectively,the total content of aryl oxygencontaining compounds(including phenolics,guaiacols,syringols and phenylates) in liquid products increases from 62 wt% to more than 72 wt%,and LTF-SG shows better catalytic performance.LTF samples have nice phase and catalytic stabilities for BL pyrolysis after five successive redox cycles.

关键词： Bagasse lignin Perovskite Catalytic pyrolysis Aryl oxygen-containing compounds Titanium-substituted lanthanum ferrite Rare earths

Directional preparation of naphthalene oil-rich tar from Beisu low-rank coal by low-temperature Catalytic pyrolysis

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Carbon Resources Conversion 2020年第1期3卷 67-75页

作者： Tao Liu Xiuli Zhang Yongzhuo Liu Lingyun Wang Qingjie Guo Key Laboratory of Clean Chemical Engineering of Colleges and Universities of Shandong Province Qingdao University of Science and TechnologyQingdao 266042People’s Republic of China State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering Ningxia UniversityYinchuan 750021People’s Republic of China

Low-rank coal(LRC)can be converted to high value-added naphthalene and its alkylated derivatives through low-temperature Catalytic pyrolysis.In this paper,the Catalytic pyrolysis of Beisu LRC in a fixed-bed at low temperature was investigated.And the catalytic effects of HZSM-5,low-temperature carbocoal(LtC),and LtC-HZSM-5 on the content and yield of naphthalene oil were examined.The results showed that the generation of naphthalene oil in low-temperature LRC pyrolysis(LT-LP)process could be improved when LtC(prepared at 550℃)or HZSM-5 was individually used as a catalyst.Compared with sole pyrolysis of raw LRC,the addition of the LtC-HZSM-5 catalyst increased the content of naphthalene oil from 11.19 wt.%to 31.49 wt%.And the yield of naphthalene oil was increased from 1.07 wt%to 5.31 wt%.The reactions of micromolecular hydrogen-containing radicals(⋅MHCR)were optimized by LtC.⋅MHCR could be captured in relatively low-temperature region(200-400℃)and released at high temperature by LtC.The generation of phenolics was inhibited by HZSM-5.As a result,the naphthalene oil-rich tar was obtained through low-temperature LtC-HZSM-5 Catalytic pyrolysis of Beisu LRC.

关键词： Naphthalene oil Low-temperature carbocoal HZSM-5 Low-rank coal Catalytic pyrolysis

Preparation of bio-oil by Catalytic pyrolysis of corn stalks using red mud

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International Journal of Agricultural and Biological Engineering 2016年第5期9卷 177-183页

作者： Wang Shaoqing Xu Meili Wang Fang Li Zhihe School of Agricultural Engineering and Food Science Shandong University of TechnologyZibo 255091China Shandong Research Center of Engineering and Technology for Clean Energy Zibo 255091China

Red mud is a solid waste residue with alkaline nature(pH>12)-originating from the Bayer process in the production of alumina,which was probed in Catalytic pyrolysis to determine its feasibility as a solid catalyst for bio-oil formulation.The red mud was characterized using X-ray fluorescence,XRD(X-ray diffraction),TG-DTG(thermogravimetry-derivative thermogravimetry),BET(surface area and pore size analyzer)measuring and testing techniques.Experiments of non-catalytic and Catalytic pyrolysis of 40-60 mesh size corn stalk powder were channelled for bio-oil production in a fixed bed reactor.It was ascertained that adding different proportions of red mud had minute influence on bio-oil production rate and product distribution.The study signaled that liquid yield from the Catalytic pyrolysis was lower than that from non-Catalytic pyrolysis.Through a series of bio-oil characterization,it was encountered that the most obviously change in the bio-oil from Catalytic pyrolysis was significant acidity reduction(pH>4).Meanwhile,the content of ketones and phenols was enhanced.Hence,the co-processing of agricultural waste and by-products alumina industry may offer an economical and environmentally friendly way of Catalytic pyrolysis with abbreviating the red mud environmental effects.

关键词： red mud Catalytic pyrolysis corn stalk powder bio-oil

Kinetics and Products Distribution Study on the catalytic Effect of Zn/HZSM-5 over pyrolysis of Chlorella through TG-FTIR and Py-GC/MS

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Journal of Thermal Science 2023年第4期32卷 1635-1643页

作者： WANG Lu YE Tao MA Xianming LIN Yan CHEN Juan WANG Fangbin MA Peiyong LIU Jian School of Food and Biological Engineering Hefei University of TechnologyHefei230009China School of Mechanical Engineering Hefei University of TechnologyHefei230009China Engineering Research Center of Bio-process Ministry of EducationHefei University of TechnologyHefei230009China

In this study,both the pyrolysis and Catalytic pyrolysis behaviour of chlorella were investigated using thermogravimetric analysis combined with Fourier Transform Infrared spectrum(TG-FTIR)and Py-GC/MS.The results of TG indicated the pyrolysis of chlorella was divided into three stages,and the Coats-Redfern kinetic model was used for the analysis and validation of the obtained thermal data.The regression coefficients indicated that the pyrolysis of chlorella was close to second-order reaction.The activation energy of pyrolysis of chlorella and Catalytic pyrolysis of chlorella+HZSM-5,chlorella+Zn/HZSM-5 was 61.645,59.080 and 56.808 kJ·mol^(−1),respectively.Combined with the data of FTIR,we found that the addition of the HZSM-5 effectively reduced the activation energy required by pyrolysis;the addition of the Zn/HZSM-5 could not only reduce the activation energy,but also reduce the yield of oxygen-containing compounds,increase the emissions of CO_(2),and facilitate the production of high value-added hydrocarbon products.These results were also verified by Py-GC/MS that the addition of Zn/HZSM-5 could reduce the formation of ketones and aldehydes and increase the production of nitrogen-containing compounds.Thus,through the Catalytic pyrolysis of chlorella,the utilization range of chlorella can be expanded,and better bio-oil can be obtained,which will play a crucial role in the selection of available energy in the future.

关键词： Catalytic pyrolysis chlorella TG-FTIR kinetic Zn/HZSM-5 Py-GC/MS

Study of Catalytic pyrolysis of Chlorella with γ-Al2O3 Catalyst

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Study of Catalytic Pyrolysis of Chlorella with γ-Al2O3 Cata...