Fast pyrolysis of waste pepper stem over waste FCC catalyst

Fast pyrolysis of waste pepper stem was investigated using waste FCC catalyst and HY zeolite with a SiO₂/Al₂O₃ ratio of 5.1. The pyrolysis oil obtained from the pyrolysis at 500 °C was analyzed using GC/MS. Oxygenates were converted, in particular when the catalyst dose was high, to furans and aromatics. The contents of low-molecular-mass phenolics and aromatics increased with increasing quantity of acid sites deployed. On the other hand, the content of high-molecular-mass phenolics was increased by catalysis with the biomass:catalyst ratio of 1:1, whereas it was decreased by catalysis with the biomass:catalyst ratio of 1:10. This was explained by the pathway of lignin-to-aromatics conversion: lignin → high-molecular-mass phenolics → low-molecular-mass phenolics → aromatics. Activated waste FCC catalyst showed a little weaker catalytic activity for the conversion of low-molecular-mass phenolics to aromatics than HY, leading to a higher phenolics content and a lower aromatics content. The results of this study indicate that the catalytic pyrolysis of lignin-rich biomass over waste FCC catalyst can be a promising way of recycling waste FCC catalyst for the production of high-value-added chemicals, such as furans, phenolics and aromatics.     

Study on pyrolysis behavior and kinetics of waste plastics with spent FCC catalyst

Pyrolysis is the most promising method for treating plastic waste since it can convert waste plastics into high value-added products, which have significant application potential. In this study, kinetic and thermodynamic analyses of spent fluid catalytic cracking (FCC) catalysts were performed for testing their applicability in catalytic cracking of mixed plastics. Thermogravimetric analysis data were obtained at different heating rates under an inert atmosphere, and the synergistic effect between the mixed plastics and activation energy reduction before and after pretreatment of the spent FCC catalysts was discussed. Through a variety of model-free methods (Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, Starink, and Kissinger methods), it is proved that the spent FCC catalyst facilitates the reduction in activation energy required for the pyrolysis of plastics, which is reduced by approximately 13% from 278 to 242 kJ/mol. The catalytic performance of spent FCC catalyst was improved after pretreatment, while its activation energy decreased by approximately 21% from 278 to 220 kJ/mol. The Friedman-Reich-Levi method was used to fit the curve, and the number of mechanism functions in plastic pyrolysis was determined according to the slope of the fitting curve. The C-R method was used in combination with the Malek method to determine the optimal mechanism function. Moreover, kinetic parameters of the spent FCC catalyst for catalytic cracking of plastics were obtained via kinetic studies on the pyrolysis of mixed plastics, which provided theoretical guidance for industrialization of plastic pyrolysis.     

提高USY型FCC催化剂硫转移和催化裂化活性的研究

采用镁、铈、镧和磷对USY型FCC催化剂进行改性,采用FT IR分析方法对改性催化剂的表面酸性进行了表征,研究了硫转移活性组分对催化剂的硫转移和催化裂化活性的影响。结果表明,多次氧化 还原循环后,改性催化剂仍保持较好的硫转移活性,可以达到60%以上。镁的引入会减少基质和分子筛表面强酸的数量,少量镁的引入对催化裂化活性影响不大,铈和镧的引入会使分子筛和基质的表面酸量得到显著增加,提高催化裂化活性,但同时会引起焦炭的增加,磷改性可改善基质和分子筛表面酸性,抑制焦炭的产生,保持催化裂化活性的同时使汽油中的烯烃质量分数下降6%。     

Influence of chemical nature and concentration of the catalyst on hydrocarbon pyrolysis

The dependence of pyrolysis rate of hydrocarbons on the concentrations of catalysts of various chemical nature has been studied. Substances active in pyrolysis can be divided into three groups: inhibiting the reaction and enhancing either its homogeneous or heterogeneous components.

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Studies on product distribution of alkali promoted iron catalyst in Fischer-Tropsch synthesis

The dependencies of hydrocarbon product distributions of alkali promoted iron catalyst in Fischer-Tropsch synthesis have been studied. The concept of two superimposed Anderson-Schulz-Flory distributions has been applied for the representation of the effects of Mg, La and Ca promoters on product distributions. The FTS performance of the catalysts was tested in a fixed bed reactor under the conditions 563 K, 1.7 MPa, H2/CO = 1 and space velocities 4.86 and 13.28 nl h-1 gFe-1 . The results indicate that approp...     

Theoretical prediction of product distribution of the pyrolysis of high density polyethylene

The main objective of this work is the formulation and development of a model that predicts the product distribution obtained in the pyrolysis of polyethylene. In order to do this a mechanistic model has been developed based on a radical mechanism. This model uses a small number of elementary kinetic steps, including initiation, β-scission, H-abstraction, aromatization and radical combination. The mechanism allows the prediction of the compounds obtained during the pyrolysis. Given the great number of species considered, the simulation of the pyrolysis process requires the solution of complex systems of ordinary differential equations. The results obtained have been validated with experimental results obtained in a free fall installation in which the pyrolysis process has been studied at different temperatures (500–1000 °C) and residence times (0.52–2.07 s).     

Theoretical prediction of product distribution of the pyrolysis of high density polyethylene

The main objective of this work is the formulation and development of a model that predicts the product distribution obtained in the pyrolysis of polyethylene. In order to do this a mechanistic model has been developed based on a radical mechanism. This model uses a small number of elementary kinetic steps, including initiation, β-scission, H-abstraction, aromatization and radical combination. The mechanism allows the prediction of the compounds obtained during the pyrolysis. Given the great number of species considered, the simulation of the pyrolysis process requires the solution of complex systems of ordinary differential equations. The results obtained have been validated with experimental results obtained in a free fall installation in which the pyrolysis process has been studied at different temperatures (500–1000 °C) and residence times (0.52–2.07 s).     

氧气对秸秆热解氮迁移与转化的影响

以秸秆为原料,在两段式固定床反应器上模拟层燃工况进行热解实验,研究了氧气对热解过程中燃料氮迁移与转化的影响。通过对焦油中含氮化合物种类与含量的GC-MS分析,提出了热解过程中燃料氮转化的反应路径,并分析了氧气的影响。与惰性气氛下相比,氧气的引入降低了焦油与焦炭的产率,从而降低了焦油与焦炭中氮的分配比,增加了气体组分中氮的分配比。以蛋白质和氨基酸作为燃料氮的禀赋形态,其在热解过程中发生一系列一次反应,生成酰胺、胺类等初级焦油产物。初级焦油发生二次反应,进一步生成腈类及含氮杂环化合物等二级焦油产物。有氧条件下,焦油中酰胺、胺类等初级焦油成分的含量显著降低,腈类及含氮杂环化合物等二级焦油成分的含量升高。     

Effect of acid strength distribution on conversion of FCC gasoline over a ZSM-5 zeolite catalyst

Summary Acid strength distribution and the distribution of aromatics formed in the FCC gasoline conversion reaction on a ZSM-5 zeolite with different Na contents have been studied. With increasing Na content in the ZSM-5 zeolite, the acid sites determined by NH₃-TPD technique, especially the strong acid sites, clearly decrease. When used as catalyst for the aromatization reaction, the transformation of olefins in the FCC gasoline into aromatics is governed directly by the strong acid sites on the ZSM-5 catalyst. Only under the conditions that a ZSM-5 catalyst possesses suitable strong acid sites is reaction temperature favorable for the aromatics formed.     

Influence of redox potential on product distribution in Clostridium thermosuccinogenes

Clostridium thermosuccinogenes are the only known anaerobic thermophilic bacteria that ferment inulin to succinate and acetate as major products and formate, lactate, and ethanol as minor products. In this study, organic acid production in 2-L fermentations having an initially low (−300 to −330 mV) or high (−220 to −250 mV) redox potential was compared for two strains of C. thermosuccinogenes (DSM 5808 and DSM 5809). Although DSM 5809 consistently provided higher succinate yield, high variability in results was attributed to the absence of redox control during the fermentations, and, therefore, fermentations at three controlled redox potentials (−240, −275, and −310 mV) were conducted. At an intermediate redox potential (−275 mV), the succinate yield was the greatest (0.36 g of succinate/g of hexose unit), whereas ethanol yield was the least (0.02 g/g). Redox potential did not significantly affect acetate or lactate formation. At controlled redox potential of −275 mV, the growth of DSM 5809 on three substrates was also compared: inulin, fructose, and glucose. DSM 5809 had similar growth rates when inulin (0.20/h) or glucose (0.21/h) was the carbon source but grew more slowly when fructose (0.16/h) was the carbon source. Also, the specific rate of utilization of fructose by DSM 5809 was higher (0.89 g of fructose/[g of biomass·h]) compared to glucose (0.53 g/[g·h]) or inulin (0.55 g/[g·h]). Succinate was the major product formed by DSM 5809 fermenting inulin (0.50 g/[g·h]) or glucose (0.36 g/[g·h]), and ethanol was the principal product when DSM 5809 fermented fructose (0.54 g/[g·h]).     

烯烃在催化裂化催化剂上反应机理的初步研究

在自制的微反-色谱装置上,进行了单体烯烃和催化裂化汽油在不同条件下的催化裂化反应实验。对单体烯烃的裂化反应规律和汽油中的烯烃在半再生催化剂和待生催化剂上的催化裂化反应规律进行对比分析。结果表明,单体烯烃反应中,C6及C6以下的烯烃主要发生骨架异构和双键异构反应,氢转移和直接裂化反应发生的较少。C7以上的烯烃95%以上发生转化,高温下直接裂化生成C3、C4,氢转移和异构化比率较大。汽油中的烯烃转化主要集中在C7以上,烯烃之间存在一定的交互作用,单体烯烃的催化裂化反应规律可以初步预测汽油中烯烃的转化。催化剂上的结焦类型对汽油中的烯烃的转化方式没有影响。     

不同气氛下煤连续热解产物的分配规律及产品品质分析

在连续进出料的流化床中研究了热解温度为850 ℃时,含有O₂、H₂、CO、CO₂、CH₄的反应气氛对热解产物分配规律及产品组成的影响。采用Raman、BET等测试方法对不同热解气氛下制得半焦的品质进行了评价,结合热重分析了影响半焦反应活性的因素。结果表明,无O₂气氛下,H₂与CO₂存在时降低了焦油产率,而CO与CH₄促进了焦油的生成。CH₄的裂解析碳使半焦产率上升。O₂的加入使CO₂、CO含量明显增加,半焦及焦油产率降低。N₂中引入O₂时,PAHs含量降低。CH₄促进了烷基萘与苯类的生成,CO则抑制酚类裂解生成苯类。CO₂的气化作用促进了微孔的生成,相应地,半焦的比表面积快速增加,半焦的反应活性也最高。CO歧化与CH₄热裂解产生的析碳堵塞了部分孔道,降低了比表面积。H₂与CH₄所产生的氢自由基能渗透到半焦内部,引起半焦结构的缩聚,进而影响氧化反应活性。     

Selective production of amylenes: Effect of catalyst alkali exchange and activation temperature on product distribution

The effect of Na-exchange and catalyst activation temperature on the selective synthesis of amylenes has been studied using a pretreated bentonite as catalyst. The selectivity to 3-methyl-1-butene rose with the catalyst activation temperatures. The alkali-exchange had a similar influence. The Na-catalyst was more selective to less substituted products, but its activity was lower than that of the acidic catalyst.

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Influence of structural factors on degradation product formation: Primary pyrolysis products of poly(acyl sulfides) investigated by direct pyrolysis mass spectrometry

Thermal degradation of two poly(acyl sulfide) polymers, poly(adipoyl sulfide) (PADS) and poly(terephthaloyl sulfide) (PTS) was investigated by direct pyrolysis mass spectrometry (DPMS). The structures of pyrolysis products detected in the DPMS analysis of both PADS and PTS indicate that the thermal degradation takes place mainly through a loss of carbon monoxide and carbonyl oxysulfide leading to the formation of cyclics. In the case of PADS, linear products with thioacid end groups were formed through hydrogen transfer reactions. In the case of PTS, almost equal proportions of linear products with phenyl end groups and cyclic products were formed. The mechanism of formation of degradation products has also been addressed.     

Alumina-supported iron catalyst - long-term study of the light product distribution in Fischer-Tropsch synthesis

Several models have been proposed to describe the carbon number product distribution and mechanism in Fischer-Tropsch synthesis (FTS). However, these models have not fully explained the product distribution and mechanism owing to the wide range and complexity of hydrocarbons in FTS. This study was conducted based on the Yao and Anderson-Schulz-Flory (ASF) carbon number product distribution models for light (C₁–C₆) hydrocarbon products of a Fe/Al₂O₃ catalyst. The product distribution based on the molar ratio of olefin to paraffin (O/P) and the neighboring olefins was also studied in order to better understand the mechanism in FTS and C₂ olefin deviation during FTS.Two sets of experiments (A and B) with different reaction conditions were conducted in microtubular fixed-bed reactors on the Fe/Al₂O₃ catalyst for 2249 h and 360 h, respectively. We found that the α values from the Yao and ASF carbon number product distribution models are relatively similar. The α values from the Yao carbon number product distribution plots are relatively constant, irrespective of the reaction conditions.Interestingly, it was also found that the secondary reactions of the C₂ olefin by re-adsorption to produce paraffins and long-chain olefins are dependent on the CO conversion and the reaction temperature during the FTS. Also, the product distribution of the neighboring olefins during the reduction condition gave a similar trend to what was observed for other reaction conditions. This result confirmed what was observed in the Yao and ASF carbon number product distribution of the olefins.     

汽油芳构化改质催化剂的覆硅改性研究

采用外表面覆硅改性,内表面金属锌改性制备了ZnS i/HZSM-5芳构化催化剂,以全馏分FCC汽油为原料,在实验室固定床反应装置上进行催化剂的抗积炭及芳构化性能评价,并探讨了催化剂改性机理。采用XRD、BET、Py-IR及元素分析等方法对催化剂晶相、孔结构、酸性及抗积炭性能进行了表征。结果表明,在500℃、1.5MPa及空速为3.0 h-1的条件下,液相产品中烯烃及芳烃质量分数分别为21.75%和27.32%,锌硅改性催化剂具有较高的活性、稳定性及芳构化降烯烃性能。     

Intramolecular Pd-catalyzed carboetherification and carboamination. Influence of catalyst structure on reaction mechanism and product stereochemistry

The intramolecular Pd-catalyzed carboetherification of alkenes affords 2-indan-1-yltetrahydrofuran products in moderate to good yield with good to excellent levels of diastereoselectivity. The stereochemical outcome of these reactions is dependent on the structure of the Pd catalyst. Use of PCy(3) or P[(4-MeO)C(6)H(4)](3) as the ligand for Pd leads to syn-addition of the arene and the oxygen atom across the double bond, whereas use of (+/-)-BINAP or DPP-benzene affords products that result from anti-addition. The catalyst-induced change in stereochemistry is likely due to a change in reaction mechanism. Evidence is presented that suggests the syn-addition products derive from an unprecedented transannular alkene insertion of an 11-membered Pd(Ar)(OR) complex. In contrast, the anti-addition products appear to arise from Wacker-type anti-oxypalladation. Studies on analogous Pd-catalyzed intramolecular carboamination reactions, which afford 2-indan-1-ylpyrrolidines that result from syn-addition, are also described.     

Effect of manganese-based pigment catalyst on CO removal during biomass pyrolysis

A commercially available black pigment was evaluated for its potential as a CO oxidation catalyst during the pyrolysis of biomass. Characterization by X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that the pigment consisted of a mixed oxide system (Cu_1.5Mn_1.5O₄–Mn₃O₄–Fe₂O₃) with an average particle size of 30–300 nm. The as received pigment catalyst was able to completely oxidize CO to CO₂ in a 4% CO–21% O₂–He gas mixture. In this study, the effect of catalyst on CO removal was evaluated during the pyrolysis of tobacco in inert and oxidizing conditions. The experiments were carried out in a flow tube reactor, which was connected to a multi-channel gas analyzer capable of measuring CO, CO₂ and O₂ concentrations. The catalyst was able to decrease the amount of CO production by 56% during the pyrolysis of biomass (tobacco) in the presence of oxygen (21% O₂–He). Oxidation of the biomass/catalyst mixture started at a lower temperature of 260 °C as opposed to a higher temperature of 300 °C in the absence of catalyst. Experiments in thermo gravimetric analyzer and differential scanning calorimeter (TG/DSC) mass spectrometer showed evidence of two-stage oxygen consumption during the pyrolysis of biomass/catalyst mixture while pure biomass pyrolized in single-stage oxygen consumption. Based on the experimental findings, a mechanism of reaction is proposed. The results show that the manganese-based mixed oxide pigment is a promising CO oxidation catalyst for biomass pyrolysis.     

Catalytic efficiency of some novel nanostructured heterogeneous solid catalysts in pyrolysis of HDPE

In the present study, the catalytic conversion of high density polyethylene (HDPE) to useful products has been investigated in the presence of BaTiO₃ based catalysts in a micro steel reactor at 350 °C and 30 min reaction time. The catalysts, including BaTiO₃, Pb/BaTiO₃, Co/BaTiO₃ and Pb–Co/BaTiO₃ were prepared in the laboratory by reactive calcination method and characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-rays (EDX), Surface Area Analyzer (SAA) and X-rays Diffractometry (XRD). The product yields (over all yields and yields of liquid, gas and coke/residue) as a function of individual catalyst concentration was studied. The result indicated a promising effect of the catalysts used on conversion to liquid products and their composition in term of carbon range (C₆ – >C₃₀) & hydrocarbon group types (paraffin's, olefins, naphthenics, and aromatics). Among the catalysts used, Pb–Co/BaTiO₃ gave the maximum yield of liquid products (86%) when used in 1 wt % loading. The same catalyst gave the average yield (20–25%) of different range hydrocarbons i.e. C₆–C₁₂, C₁₃–C₁₆, C₁₇–C₂₀ and C₂₀–C₃₀. Inversely, the un-doped BaTiO_3, favored the formation of C₆–C₁₂ and C₁₃–C₁₆ range hydrocarbons, whereas Pb doped BaTiO₃ and Co doped BaTiO₃ enhanced the yield of C₁₃–C₁₆, and C₂₀–C₃₀ range hydrocarbons. Regarding the hydrocarbon group types, all catalysts significantly increased the formation of paraffins and reduced olefins and naphthenes.