3种过渡金属氧化物对生物质微波快速催化热解产物的影响

以3种过渡金属氧化物Fe2O3,Co3O4,NiO为催化剂,HZSM-5为载体,在微波反应器中对3种典型生物质原料松木、水曲柳和玉米芯快速催化热解。对气、液、固3相热解产物的产率计算结果表明,松木和水曲柳的热解液相产率均比玉米芯高8%左右,Co3O4/HZSM-5有利于液相产率提高,最高可达45.4%(水曲柳)。对液相成分的GC-MS分析表明,所用催化剂均对生物质原料具有良好的脱氧效果,可降低液相产物中酸、醛、酮含量。各催化剂均能大幅提高芳香族化合物产率,其中Co3O4/HZSM-5作用最为明显,最高可达49.61%(松木);且均能促进G型酚与S型酚生成结构更稳定的H型酚,NiO/HZSM-5作用尤为明显,最高产率可达31.64%(玉米芯),有利于产物的富集;Fe2O3/HZSM-5可促进定向热解,对糠醛产率具有较为明显的提高作用,其中玉米芯糠醛产率高达13.61%。     

内循环串行流化床生物质催化热解试验研究

在处理量为0.2 kg/h的新型内循环串行流化床(IIFB)上进行了生物质催化热解制油的试验研究.以木屑为原料、石英砂为热载体,研究了在没有催化剂条件下反应温度对热解产物分布的影响;以HZSM-5催化剂与石英砂混合物为床料进行了催化热解试验,并对热解产物和反应后的催化剂进行了表征分析.结果表明:反应温度为515℃时,液体产物的收率最高.HZSM-5催化剂的加入促进了气体以及焦炭的生成,使液体产物的收率降低,且催化剂体积分数越大,影响越显著.催化荆表面的积炭经燃烧反应后被除去,催化剂的稳定性得到改善.热解不可冷凝气体的主要成分为CO和CO2,随着热解温度的升高,CO2产量下降,CO和CH4的产量增加.经HZSM-5催化热解后,生物油中的酸、醛和酮类物质含量明显减少,而小分子的烃类与酚类物质含量明显增加,表明催化剂具有明显的脱氧效果.     

生物质催化热解的TG-FTIR研究

借助综合热分析仪和傅立叶红外联用技术(TG-FTIR),考察了HUSY、REY和HZSM-53种分子筛以及重油催化裂化催化剂MLC和馏分油催化裂解催化剂CIP对生物质催化热解的活性和选择性。研究结果表明,分子筛对生物质热解产物的脱氧活性顺序为:REY≈HUSY>HZSM-5,生成高辛烷值烃类的选择性顺序为:REY>HUSY≈HZSM-5;MLC催化剂和CIP催化剂都表现出较高的选择活性,前者的脱氧活性略高于后者;择形分子筛HZSM-5的引入对调整催化剂酸强度、提高催化转化选择性和抑制焦炭生成产生一定作用。     

纤维素催化热解定向调控制取不含氧烃类液体燃料

为了将生物质能高效转化为高品位不含氧的液体燃料,以纤维素为例,研究了以催化热解方式将热解产物转化为芳香烃类液体燃料的过程.实验发现,纤维素热解产生的含氧有机小分子,可以通过催化热解的形式高效转化为不含氧的芳香烃类液体.催化剂采用HZSM-5(23)、催化剂原料质量比例为5∶1、热解温度为650℃、升温速率为10000 K/s的工况为纤维素催化热解的最佳工况,单环芳烃、多环芳烃产率分别为9.90%和12.91%,总芳香烃类产率为22.81%.热解温度提升至650℃前,更高的热解温度能获得更高的芳香烃产率.继续提高热解温度,单环芳烃、多环芳烃分子间还可能进一步发生聚合反应,最终产生积碳.同时本文也提出了一种可行的纤维素催化热解中的反应途径,与本文实验结果较为匹配.     

Fe_2O_3/γ-Al_2O_3催化裂解生物质制氢研究

在自行研制的生物质连续热解反应装置上进行了稻壳连续热解和二次催化裂解制氢试验研究,所用Fe_2O_3/γ-Al_2O_3催化剂采用浸渍法制备。考察了Fe/Al催化剂焙烧温度及二次催化裂解温度对裂解气中H_2含量和裂解液体组分的影响。试验结果表明:Fe_2O_3/γ-Al_2O_3催化剂对H_2有较大的选择性,当Fe/Al=0.7、催化剂焙烧温度为550℃、二次裂解温度为700℃时,H_2产率达到34.8%;稻壳直接二次裂解液体产物中主要为醋酸,含量达49.44%,催化裂解后主要为丙酮,含量达到50.56%。     

改性HZSM-5对油茶籽壳催化热解特性的影响

为改善油茶籽壳热解产物分布和油茶籽壳生物油成分特性,制备了金属Co、Mg和Cu改性的HZSM-5并用于油茶籽壳催化热解.对改性后的HZSM-5进行了表征,表征结果显示改性后的HZSM-5微观形貌没有改变,但比表面积有了较大幅度的降低.金属Mg负载改性的HZSM-5有利于油茶籽壳热解产生更多的液相产物,而金属Cu负载改性的HZSM-5则有利于油茶籽壳热解产生更多的气相产物.金属Co和Cu改性的HZSM-5提高了油茶籽壳热解生物油中酚类的相对含量,降低了生物油中酸类物质的相对含量.     

碱改性HZSM-5热解生物质模型化合物影响研究

实验采用Py-GC/MS在500 ℃下对NaOH、Na₂CO₃和有机碱（CTAB/TPAOH）改性HZSM-5催化热解生物质模型化合物的产物分布影响机制进行探究。结果表明,利用0.1 mol/L NaOH/Na₂CO₃改性HZSM-5使热解油中小分子酮、酚和酯类物质的收率有所提高,有利于碳链长度≥5产物（C_≥5）的生成;0.2 mol/L NaOH/Na₂CO₃改性HZSM-5催化剂有助于脱羰和脱羟基反应的进行,促使环状化合物开裂转化为链状化合物。TPAOH的加入使NaOH改性HZSM-5催化热解产物中酮类产物收率降至18.56%、醛类产物收率增至3.01%,并促使C_≥9产物向C_≤4转化,链状产物增加;经CTAB改性后C_≥9产物向C_5-8转化,环状产物增加。     

负载型HZSM-5对紫茎泽兰微波催化热解产物的影响

随着化石能源的消耗及环境条件的恶化,寻找新的可替代能源已经成为整个社会面临的重大难题.文中试验以世界性恶性杂草紫茎泽兰为原料,讨论了天然催化剂以及负载型HZSM-5催化剂对生物质微波催化热解的产物的影响.结果表明:凹凸棒土对酸类加氢还原反应具有较强的催化作用,使产物中羰基类物质含量增加.而HZSM-5催化剂能够促进芳香...     

双金属共改性沸石催化杉木热解制备轻质芳烃

以杉木为原料在金属改性分子筛作用下进行热解制备芳烃,采用热裂解-气相色谱质谱法进行热解。结果表明：单金属改性中5%Zn/HZSM-5可达到最好催化效果,其芳烃的相对峰面积达到最高的34.17%,苯、二甲苯的产率相对最高;与单金属改性相比,1%Zn-4%Co/HZSM-5可增大单环芳烃产率,其中苯增大1.19倍,甲苯增大1.21倍;萘、甲基萘等大分子芳烃产率显著减小,同时氧化物产率减少。验证不同金属结合会产生某种协同效应,在热解过程中添加双金属改性分子筛有利于热解油品位的提高。通过NH₃-TPD表征和BET测试阐述金属改性对催化剂表面结构及酸位点变化的影响。     

基于镓改性ZSM-5分子筛作用下的环氧树脂催化热解制芳烃反应性能研究

为实现环氧树脂的清洁处置与资源化利用,在一系列金属镓改性的ZSM-5催化体系中进行快速热解实验,并进行了包括氮气吸附-脱附测试、X射线衍射（XRD）、氨气程序升温吸附（NH₃-TPD）、热重分析（TGA）和透射电镜（TEM）在内的全面的催化剂表征,以阐明催化剂的结构特性。镓的改性显著调节了ZSM-5分子筛的布朗斯特/路易斯酸分布和孔隙结构,改善了高温下分子筛的热解脱氧性能,提高了催化剂的择形催化能力。选取镓负载量、热解温度、催化剂用量、热解升温速率和催化剂回用次数为实验变量,探究了热解油组成分布的变化规律。结果表明,与未改性的分子筛相比,镓改性的ZSM-5分子筛显著提高了环氧树脂快速热解过程中芳烃的选择性。通过不同热解条件的研究发现,环氧树脂催化热解制备芳烃的最佳条件为：1Ga-ZSM-5分子筛∶环氧树脂 = 1∶1,热解温度为600℃,热解速率为10℃/ms,此时芳烃总选择性最高可达56.4%,其中更有价值的单环芳烃的相对含量达到31.6%。     

HZSM-5催化纤维素液化的研究

以微晶纤维素为研究对象,HZSM-5为催化剂,系统考察了原料/溶剂水质量比、反应温度、反应时间、催化剂用量、催化剂硅铝比等对催化液化效果的影响。结果表明:在纤维素/溶剂水的质量比为1/20、反应温度280℃、反应时间40min、HZSM-5催化剂(硅铝比为28)用量为原料质量分数的5%时,可以得到较好的催化液化效果,且HZSM-5催化剂可以多次重复使用。     

Catalytic Oligomerization of ethylene over nano-sized HZSM-5

The nano-sized HZSM-5 zeolites with different Si/Al ratios were pretreated, characterized, and tested in ethylene oligomerization performed in a fixed-bed reactor under relatively mild conditions. The effects of catalyst acidity and reaction temperature on the activity, selectivity and stability were investigated, and a possible reaction route of ethylene over acidic sites of nano-sized HZSM-5 catalyst was proposed. In comparison with micro-sized HZSM-5 zeolite, nano-sized HZSM-5 zeolites exhibited higher activity and better resistance to deactivation. Under optimal conditions (T = 275–300 °C, P = 3.0 MPa, WHSV = 1.0 h⁻¹), The average ethylene conversion was 62.5% over the nano-sized HZSM-5 with an Si/Al ratio of 80, while the selectivity to C₄₊ olefins and α-olefins was 64.3% and 13.3%, respectively. Furthermore, the products of ethylene oligomerization were a complex hydrocarbon mixture due to the acid-catalyzed secondary reactions, for which the distribution of even and odd numbered carbon atoms formed a continuous volcanic shape mainly centered on C₆–C₁₀. Furthermore, these tests demonstrate that the activity and selectivity of ethylene oligomerization depend on the operating conditions and the acidity of the catalysts. These results indicate that the Brønsted acid sites may be mainly responsible for secondary reactions and deactivation of the catalyst, whereas the Lewis acid sites may be more advantageous for ethylene oligomerization.     

Preparation of bio-oil derived from catalytic upgrading of biomass vacuum pyrolysis vapor over metal-loaded HZSM-5 zeolites

The Fe-, Co-, Cu-loaded HZSM-5 zeolites were prepared via impregnation method. The upgrading by catalyst on biomass pyrolysis vapors was conducted over modified zeolites to investigate their catalytic upgrading performance and anti-coking performance. The Brønsted acid sites amount on Cu-,Co-loaded HZSM-5 decreased sharply, while that of Lewis both increased. The yield of liquid fraction and refined bio-oil over metal loaded ZSM-5 catalysts decreased, while that of char almost kept constant. The physical property of refined bio-oil was promoted in terms of pH value, dynamic viscosity and higher heating value (HHV). FT-IR analysis revealed that the chemical structure of refined bio-oil obtained over Fe-, Co-, Cu-loaded HZSM-5 zeolites was highly similar. The yield of monocyclic aromatic and aliphatic hydrocarbon over Fe-,Co-loaded HZSM-5 were boosted by around 2.5 times compared with original ZSM-5 zeolites. Data analysis revealed that Cu/HZSM-5 presented the worst deoxygenation ability. The anti-coking capability of Fe/HZSM-5 was obviously better, i.e., the coke content showed an approximate decrease of 38%. Thus, this study provided an efficient Fe/HZSM-5 catalysts for preparation of bio-oil derived from catalytic upgrading of biomass pyrolysis vapor.     

Catalytic upgrading pyrolysis vapors of Jatropha waste using metal promoted ZSM-5 catalysts: An analytical PY-GC/MS

HZSM-5 with high surface area of 625 m²/g was successfully synthesized by hydrothermal method at 160 °C for 72 h. The metal promoted on HZSM-5 catalyst was prepared by liquid ion exchange method. From XRD results, the addition of metals such as Co and Ni did not change the HZSM-5 structure. The metal/HZSM-5 showed lower crystallinity and surface area than the parent HZSM-5 because of the metal dispersion on the HZSM-5 surface. The metal contents of Co/HZSM-5 and Ni/HZSM-5 detected by EDX were less than 1 wt%. Catalytic fast pyrolysis of Jatropha waste using HZSM-5 and metals/HZSM-5 was investigated in terms of biomass to catalyst ratios (1:0, 1:1, 1:5 and 1:10) and types of metals (Co and Ni). From the results, it can be concluded that both biomass to catalyst ratios and the presence of metals had an effect on the increase in aromatic hydrocarbons yields as well as the decrease in the oxygenated and N-containing compounds. Both Co/HZSM-5 and Ni/HZSM-5 promoted the production of aliphatic compounds. Additionally, the PAHs compounds such as napthalenes and indenes, which caused the formation of coke, could be inhibited by metal/HZSM-5, particularly, Ni/HZSM-5. Among catalysts, Ni/HZSM-5 showed the highest hydrocarbon yield of 97.55% with N-containing compounds remained only 1.78%. The formation of hydrocarbon compounds increased the heating values of bio-oils while the elimination of the undesirable oxygenated compounds such as acids and ketones could alleviate problem regarding acidity and instability in bio oils.     

Development of a bifunctional Ni/HZSM-5 catalyst for converting prairie cordgrass to hydrocarbon biofuel

Ni/HZSM-5 catalysts were prepared using the impregnation method. The HZSM-5 and impregnated Ni/HZSM-5 catalysts were characterized by Brunauer–Emmett–Teller and X-ray diffraction. The HZSM-5 and Ni/HZSM-5 catalysts were used for prairie cordgrass (PCG) thermal conversion in a two-stage catalytic pyrolysis system. The products contained gas, bio-oil, and bio-char. The gas and bio-oil were analyzed by gas chromatography and gas chromatography–mass spectrometry separately. Higher heating values and elemental composition of bio-char were determined. The results indicated that 12% Ni/HZSM-5 treatment yielded the highest amount of gasoline fraction for hydrocarbons and showed a robust ability to upgrade bio-oil vapor.     

Integrated production of aromatic amines,aromatic hydrocarbon and N-heterocyclic bio-char from catalytic pyrolysis of biomass impregnated with ammonia sources over Zn/HZSM-5 catalyst

By introducing exogenous nitrogen during biomass pyrolysis under nitrogen-rich conditions, high-value nitrogen-containing products, i.e., nitrogen-rich char and oil may be produced. Based on the cogeneration of high-value nitrogen products from biomass, biomass nitrogen-enriched pyrolysis was performed in a fixed bed with different sources and contents of ammonia. The yields, composition and characteristics of the products were investigated. Moreover, the formation mechanism of N-containing species was explored in depth for the pyrolysis and catalytic pyrolysis with HZSM-5 and Zn/HZSM-5 catalysts via elemental analysis, XPS, FTIR and BET. The results showed that ammonia impregnation could promote a Maillard reaction, reduce the content of small aldehydes and ketones, and produce a nitrogen-enriched bio-oil. The contents of N-containing species and phenolic substances in the pyrolysis oil of biomass impregnated with 10% urea reached 15.66% and 56.69%, respectively. Moreover, the nitrogen on the coke surface after pretreatment was mainly composed of CN, CN and NCOO functional groups. The bio-char generated abundant pyridinic-N, pyrrolic-N, quaternary-N, and pyridone-N oxides. The presence of urea introduced many alkaline N-containing functional groups on the surface of the bio-char and promoted the transformation of nitrogen from amides and imides to heterocyclic nitrogen with higher thermal stability. Furthermore, Zn was an excellent catalyst for the Maillard reaction, and the Zn/HZSM-5 catalyst had a higher selectivity for aromatic hydrocarbons (96.98% for biomass and 86.48% for urea/biomass) and N-containing heterocyclic compounds, such as indoles (6.16% for biomass and 13.51% for urea/biomass). Additionally, the coke content decreased, and the catalyst deactivation decreased.     

Fast and catalytic pyrolysis of xylan: Effects of temperature and M/HZSM-5 (M= Fe,Zn) catalysts on pyrolytic products

Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was employed to achieve fast pyrolysis of xylan and on-line analysis of pyrolysis vapors. Tests were conducted to investigate the effects of temperature on pyrolytic products, and to reveal the effect of HZSM-5 and M/HZSM-5 (M= Fe, Zn) zeolites on pyrolysis vapors. The results showed that the total yield of pyrolytic products first increased and then decreased with the increase of temperature from 350°C to 900°C. The pyrolytic products were complex, and the most abundant products included hydroxyacetaldehyde, acetic acid, 1-hydroxy-2-propanone, 1-hydroxy-2-butanone and furfural. Catalytic cracking of pyrolysis vapors with HZSM-5 and M/HZSM-5 (M= Fe, Zn) catalysts significantly altered the product distribution. Oxygen-containing compounds were reduced considerably, and meanwhile, a lot of hydrocarbons, mainly toluene and xylenes, were formed. M/HZSM-5 catalysts were more effective than HZSM-5 in reducing the oxygen-containing compounds, and therefore, they helped to produce higher contents of hydrocarbons than HZSM-5.     

Fast and catalytic pyrolysis of xylan: Effects of temperature and M/HZSM-5 (M = Fe, Zn) catalysts on pyrolytic products

Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) was employed to achieve fast pyrolysis of xylan and on-line analysis of pyrolysis vapors. Tests were conducted to investigate the effects of temperature on pyrolytic products, and to reveal the effect of HZSM-5 and M/HZSM-5 (M = Fe, Zn) zeolites on pyrolysis vapors. The results showed that the total yield of pyrolytic products first increased and then decreased with the increase of temperature from 350°C to 900°C. The pyrolytic products were complex, and the most abundant products included hydroxyacetaldehyde, acetic acid, 1-hydroxy-2-propanone, 1-hydroxy-2-butanone and furfural. Catalytic cracking of pyrolysis vapors with HZSM-5 and M/HZSM-5 (M = Fe, Zn) catalysts significantly altered the product distribution. Oxygen-containing compounds were reduced considerably, and meanwhile, a lot of hydrocarbons, mainly toluene and xylenes, were formed. M/HZSM-5 catalysts were more effective than HZSM-5 in reducing the oxygen-containing compounds, and therefore, they helped to produce higher contents of hydrocarbons than HZSM-5.     

Selective catalytic fast pyrolysis of Jatropha curcas residue with metal oxide impregnated activated carbon for upgrading bio-oil

Jatropha curcas waste was subjected to catalytic pyrolysis at 873 K using an analytical pyrolysis–gas chromatography/mass spectrometry in order to investigate the relative effect of various metal oxide/activated carbon (M/AC) catalysts on upgrading bio-oil from fast pyrolysis vapors of Jatropha waste residue. A commercial AC support was impregnated with Ce, Pd, Ru or Ni salts and calcined at 523 K to yield the 5 wt.% M/AC catalysts, which were then evaluated for their catalytic deoxygenation ability and selectivity towards desirable compounds. Without a catalyst, the main vapor products were fatty acids of 60.74% (area of GC/MS chromatogram), while aromatic and aliphatic hydrocarbon compounds were presented at only 11.32%. Catalytic pyrolysis with the AC and the M/AC catalysts reduced the oxygen-containing (including carboxylic acids) products in the pyrolytic vapors from 73.68% (no catalyst) to 1.60–36.25%, with Ce/AC being the most effective catalyst. Increasing the Jatropha waste residue to catalyst (J/C) ratio to 1:10 increased the aromatic and aliphatic hydrocarbon yields in the order of Ce/AC > AC > Pd/AC > Ni/AC, with the highest total hydrocarbon proportion obtained being 86.57%. Thus, these catalysts were effective for deoxygenation of the pyrolysis vapors to form hydrocarbons, with Ce/AC, which promotes aromatics, Pd/AC and Ni/AC as promising catalysts. In addition, only a low yield (0.62–7.80%) of toxic polycyclic aromatic hydrocarbons was obtained in the catalytic fast pyrolysis (highest with AC), which is one advantage of applying these catalysts to the pyrolysis process. The overall performance of these catalysts was acceptable and they can be considered for upgrading bio-oil.     

Production of aromatic compounds from catalytic fast pyrolysis of Jatropha residues using metal/HZSM-5 prepared by ion-exchange and impregnation methods

Metal based-zeolite catalysts were successfully prepared by two different methods including ion-exchange and wet impregnation. HZSM-5 synthesized by hydrothermal method at 160 °C was used as a support for loading metals including Co, Ni, Mo, Ga and Pd. The metal/HZSM-5 had surface area and pore size of 530–677 m²/g and 22.9-26.0 Å. Non- and catalytic fast pyrolysis of Jatropha residues using metal/HZSM-5 were studied using an analytical pyrolysis-GC/MS at 500 °C. Non-catalytic pyrolysis vapors contained primarily high levels acid (50.7%), N-containing compounds (20.3%), other oxygenated compounds including ketones, alcohols, esters, ethers, phenols and sugars (25.0%), while generated small amount of aromatic and aliphatic hydrocarbons of 3.0% and 1.0%. The addition of synthesized metal/HZSM-5 improved the aromatic selectivity up to 91–97% and decreased the undesirable oxygenated (0.6–4.0%) and N-containing compounds (1.8–4.6%). The aromatic selectivity produced by metal-ion exchanged catalysts was slightly higher than that produced by impregnated ones. At high catalyst content (biomass to catalyst ratio of 1:10), Mo/HZSM-5 showed the highest aromatic selectivity of 97% for ion-exchanged catalysts and Ga/HZSM-5 revealed the highest aromatics of 95% for impregnated catalysts. The formation of aromatic compounds could be beneficial to improve calorific values of bio-oils. The presence of metal/HZSM-5 from both preparation methods greatly enhanced MAHs selectivity including benzene, toluene, and xylene (BTX), while substantially reduced unfavorable PAHs such as napthalenes.