Formation of coke in thermal cracking of jet fuel under supercritical conditions

Continuous-flow reactor experiments were carried out to study coke formation from thermal cracking of home-made jet fuel RP-3 under supercritical conditions. The mechanism and precursor of coke forming were analyzed. The starting cracking temperature of RP-3 fuel was determined to be 471.8°C by differential scanning calorimetry (DSC). Temperature-programmed oxidation and scanning electron microscopy (SEM) characterizations of the stressed tubes showed that there are three different coke species including chemisorbed carbon, amorphous carbon and filamentous coke in the solid deposits. More than 90% of coke deposits are carried away by the supercritical fluid, which has strong capabilities of extraction for coke deposits and their precursors. There were 17.1 wt-% of iron and 11.1 wt-% of chromium found on the coke surface detected by energy dispersive spectroscopy (EDS) which suggests carburetion on alloy. RP-3 fuel and its cracking liquids were analyzed by GC-MS,which showed that the content of alkyl benzene and alkyl naphthalene increased evidently in cracking liquids.     

Catalytic cracking of endothermic fuels in coated tube reactor

Suspensoid of HZSM-5 or HY zeolites mixed with a self-made ceramic-like binder was coated on the inner wall of a tubular reactor by gas-aided fluid displacement technology. The coated zeolites were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The coating thickness is 10–20 μm and the particle size of the zeolites is in the range of 1–5 μm. In the coated reactor, cracking of endothermic fuels including n-dodecane and aviation fuel RP-3 was carried out separately under supercritical conditions at 600°C and 625°C to investigate their heat sinks and conversion of catalytic reactions. For the reaction catalyzed by HY (25% mass fraction) coating, the heat sink capacity of n-dodecane are 815.7 and 901.9 kJ/kg higher than that of the bare tube at 600°C and at 625°C, respectively. Conversion of n-dodecane also increases from 42% to 60% at 600°C and from 66% to 80% at 625°C. The coated zeolite can significantly inhibit the carbon deposition during supercritical cracking reactions. __________ Translated from Petrochemical Technology, 2007, 36(4): 328–333 [译自: 石油化工]     

Catalytic cracking of endothermic fuels in coated tube reactor

Suspensoid of HZSM-5 or HY zeolites mixed with a self-made ceramic-like binder was coated on the inner wall of a tubular reactor by gas-aided fluid displacement technology. The coated zeolites were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The coating thickness is 10–20 ?m and the particle size of the zeolites is in the range of 1–5 ?m. In the coated reactor, cracking of endothermic fuels including n-dodecane and aviation fuel RP-3 was carried out separately under supercritical conditions at 600°C and 625°C to investigate their heat sinks and conversion of catalytic reactions. For the reaction catalyzed by HY(25% mass fraction) coating, the heat sink capacity of n-dodecane are 815.7 and 901.9 kJ/kg higher than that of the bare tube at 600°C and at 625°C, respectively. Conversion of n-dodecane also increases from 42% to 60% at 600°C and from 66% to 80% at 625°C. The coated zeolite can significantly inhibit the carbon deposition during supercritical cracking reactions.     

碳氢燃料热裂解与引发裂解换热对比实验

通过流动管反应器对碳氢燃料RP-3在超临界条件下的热裂解及引发裂解进行了实验,对两种条件下的燃料吸热能力及传热特性进行了对比分析,并对裂解产物进行了采样分析。结果表明,引发裂解降低了燃料的裂解起始温度,在一定温度区间内提高了燃料的裂解率,从而有效提高了燃料热沉,在相同热通量条件下,降低了燃料温度,并降低了加热段壁面温度。对流换热受化学反应及物性变化的影响,燃料裂解吸热可增强换热,而大量气态产物的生成会降低换热,因此,裂解反应的增强不一定增强换热。     

Understanding the chemical reaction and mass-transfer phenomena in a recirculating enzymatic membrane reactor for green ester synthesis in ionic liquid/supercritical carbon dioxide biphasic systems

The synthesis of butyl propionate in a recirculating bioreactor in room temperature ionic liquid/supercritical carbon dioxide biphasic systems at 50 °C and 80 bar was studied. In these systems, α-alumina microporous membranes with immobilized Candida antarctica lipase B were coated with four different ionic liquids based on 1-n-alkyl-3-imidazolium cations and hexafluorophosphate and bis{(trifluoromethyl)sulfonyl}imide anions. Selectivity increased (reaching >99.5%) when room temperature ionic liquid/supercritical carbon dioxide biphasic systems were used rather than in supercritical carbon dioxide alone. To understand the behaviour of the enzyme and the mass-transfer phenomena in these biphasic systems, the reaction was also carried out in ionic liquids and in ionic liquid/hexane biphasic systems, and the ionic liquid/hexane partition coefficients of the compounds involved in the transesterification reaction were determined. It was observed that the activity in room temperature ionic liquid/supercritical carbon dioxide biphasic systems depends on the effect of the ionic liquid media on the enzyme and the diffusional limitations across the IL-layer around the biocatalyst.     

Cracking of n-dodecane during supercritical state on HZSM-5 membranes

In the new generation of aircraft, jet fuel will serve as both an energy source and a heat sink for cooling through endothermic fuel reactions. Catalytic cracking of hydrocarbon fuel has proved to be potential for endothermic reaction. For this application, we have prepared ZSM-5 membranes as catalyst on the surface of stainless steel by secondary growth method. An optimized activation procedure of ZSM-5 membrane for catalytic cracking reaction is established by combining the results of catalytic reaction with thermal analysis (TGA and DSC). Taking n-dodecane as a model compound, the influence of silica alumina ratio (SAR = nSiO₂/Al₂O₃) of initial gel on the activity of hydrocarbon cracking reaction were studied. The results also demonstrate that the conversion of catalytic cracking reaction is much higher than that of pyrolysis during supercritical state. In addition, hydrogen molar ratio in gas production decreases with increasing the reaction temperature. Besides that, the optimum temperature for coke removal and the reduction of zeolite catalysts is between 550 °C and 600 °C.     

The chemical nature of a supercritical gas extract including comparison with other coal liquids

A supercritical gas extract of an Australian bituminous coal was separated into oil, asphaltene and pre-asphaltene. The oil was further separated by chromatography into three fractions. Average structure data for each fraction are reported based on NMR spectroscopy combined with elemental, molecular weight and functional group analyses. Unsubstituted alkyl chains (> C₈) were found in every fraction of the extract. The presence of n-alkanes, 1-alkenes and phenyl-n-alkanes were shown. The supercritical gas extract was compared with a flash pyrolysis tar and with hydrogenation liquids from the same coal. The supercritical gas extract and the flash pyrolysis tar had a similar distribution between oil, asphaltene and pre-asphaltene, but the oil, asphaltene and pre-asphaltene from the supercritical gas extract were less aromatic and contained fewer heteroatoms than these fractions from the flash pyrolysis tar. The supercritical gas extract has a higher H/C atomic ratio, higher heteroatom content and a higher percentage of carbon in long unsubstituted alkyl chains than hydrogenation liquids produced at 400°C and 450 °C. The oil/asphaltene ratio and the aromaticity of the oil and asphaltene from the supercritical gas extract were intermediate between those obtained for the two hydrogenation liquids.     

醋酸钾对轻石脑油裂解结焦的影响

为考察碱金属元素对裂解结焦的影响,以醋酸钾为结焦抑制剂,在850℃下对退役25Cr35Ni炉管试样内表面进行了结焦实验。利用扫描电子显微镜(SEM)、场发射扫描电镜(FE-SEM)、能量色散谱仪(EDS）、X射线衍射(XRD)和Raman光谱对退役25Cr35Ni炉管试样内表面和焦层进行了表征。结果表明,退役25Cr35Ni炉管内表面主要由Cr_1.3Fe_0.7O₃相似文献   

Diels–Alder Reaction of Cyclopentadiene and Alkyl Acrylates in the Presence of Pyrrolidinium Ionic Liquids with Various Anions

Abstract  

The conversion and stereoselectivity of transformation to endo and exo norbornene derivatives was determined in the Diels–Alder reaction of cyclopentadiene with alkyl acrylates. The reactions were carried out in the pyrrolidinium ionic liquids in the presence of metal chlorides and trifluoromethanesulfonates as the catalysts. Shorter reaction times and higher conversions of dienophile were observed in a comparison with analogous cycloadditions carried out in the presence of conventional organic solvents. A higher stereoselectivity to the endo isomer was found in the majority of cases. The ionic liquids composed of 1-butyl-1-methylpyrrolidinium cation (Pyrr_1.4) and various anions were used. The influence of ionic liquid anion and several metal chlorides and metal triflates used as the catalysts on the conversion was determined.     

活塞式航空发动机燃用生物航煤与RP-3燃料的适用性对比

以大豆油为原料，经催化裂解、精馏、芳构化和加氢过程制备生物航煤，并分析了其组成及理化性能；进一步采用活塞式航空发动机进行发动机台架试验，对比分析了生物航煤与RP-3燃料的燃用适用性。研究结果表明：生物航煤的基本组成为直链烷烃74.54%、环烷烃13.04%、芳香烃10.31%、醚类1.07%和非α-链烯烃1.04%；生物航煤的热值较高(44.4 MJ/kg)，冰点低(-48 ℃)，但黏度较高(2.11 mm²/s)。与RP-3燃料相比，生物航煤具有更低的启动温度；温升速度(相差4 ℃之内)、油耗(相差小于0.02 g/s)与RP-3燃料接近，当发动机转速超过4 200 r/min时，过量空气系数波动较大(0.8~1.2)，燃烧状态恶化。台架试验后发动机拆解检查发现，燃用生物航煤后出现结焦积炭现象，这是由于该批次生物航煤黏度较大(>2 mm²/s)，对雾化效率、燃烧充分程度等发动机工作性能产生影响。     

The pyrolysis of propane. I. Production of gases,liquids and carbon

Studies have been carried out on the formation of gases, tars and carbon from the pyrolysis of propane under conditions pertinent to steam cracking. Careful analysis has been carried out to relate the production of gases, liquids and solids in the presence and absence of hydrogen and helium diluents. The experimental observations agree with predictions of gas production from a mathematical model. The reactor surface is shown to influence the production of carbon and possibly the production of gases and tars. Minimisation of coke formation in steam cracking is shown to depend, at least in part, on the correct choice of material for reactor construction.     

Recovery of oil <Emphasis Type="Italic">via</Emphasis> acid-catalyzed transesterification

The process of preparing oil palm seed for planting generates vast quantities of waste pulp. The pulp (ca 80% oil), for which no use has been found, is indiscriminately dumped because either reprocessing it into a useful product or disposing of it properly is expensive. In situ transesterification of the pulp with methanol and ethanol using sulfuric acid as catalyst was carried out on a laboratory scale. Our aim was to develop a process to recover the largely hydrolytically degraded oil (PV, 25–26; FFA, 25–26%) from the pulp. Acid-catalyzed conversions of the oil into alkyl esters were 96–97% for both methanol and ethanol. The accompanying concentrations of FFA, TG, DG, and MG were low. The identities and proportions of FA ester in the alkyl esters reflected the FA content of the palm oil. The values for the esterified products of some fuel properties such as cloud point and viscosity were slightly below the general current specification. However, with optimization of the reaction conditions and simplification of some of the technical aspects, the waste pulp could be a good source of alkyl esters for both oleochemical and fuel applications.     

Hydrotreating of light gas oil using a NiMo catalyst supported on activated carbon produced from fluid petroleum coke

Nitric acid functionalized steam activated carbon (NAFSAC) was prepared from waste fluid petroleum coke (FPC) and used as a support material for the synthesis of a NiMo catalyst (2.5 wt-% Ni and 13 wt-% Mo). The catalyst was then used for the hydrotreatment of light gas oil. The support and catalysts were characterized by Brunauer-Emmett-Teller (BET) gas adsorption method, X-ray diffraction, H₂-temperature programmed reduction, NH3-temperature programmed desorption, CO-chemisorption, mass spetrography, scanning electron microscopy (SEM), Boehm titration, and Fourier transform infrared spectroscopy (FTIR). The SEM results showed that the carbon material retained a needle like structure after functionalization with HNO₃. The Boehm titration, FTIR, and BET results confirmed that the HNO₃ functionalized material had moderate acidity, surface functional groups, and mesoporosity respectively. The produced NAFSAC had an inert nature, exhibited the sink effect and few metal support interactions, and contained functional groups. All of which make it a suitable support material for the preparation of a NiMo hydrotreating catalyst. Hydrotreating activity studies of the NiMo/NAFSAC catalyst were carried out under industrial operating conditions in a laboratory trickle bed reactor using coker light gas oil as the feedstock. A parallel study was performed on the hydrotreating activity of NiMo/γ-Al₂O₃ as a reference catalyst. The hydrodesulfurization and hydrodenitrogenation activities of the NiMo/NAFSAC catalyst were 62% and 30%, respectively.     

Catalytic cracking of n-dodecane over HZSM-5 zeolite under supercritical conditions: Experiments and kinetics

The catalytic cracking of n-dodecane over HZSM-5 zeolite catalyst was investigated at 400–450 °C under supercritical and subcritical pressures (0.1–4.0 MPa). The results show that both the activity of the catalyst and its stabilization towards deactivation decrease with increasing pressure, and the catalyst maintains substantially higher activity when feed rate exceeds 4.00 ml/min under supercritical conditions. A first-order Langmuir kinetic model with a novel decay function is developed for the supercritical catalytic cracking of hydrocarbon incorporating supercritical extraction effect on catalyst stability, which is satisfactory to describe the kinetic behaviors of catalytic cracking of supercritical n-dodecane. According to the estimated reaction rate and adsorption constant of n-dodecane on HZSM-5 at different temperature, the activation energy of 125.4 kJ/mol and adsorption heat 109.5 kJ/mol were calculated. An index of CRSE is proposed to define contribution ratio of supercritical extraction to the activity of the HZSM-5 catalyst in the developed kinetics model, and it is found that the CRSE increases with increasing hydrocarbon feed rates and decreasing catalytic activities, and reaches maximum value when the coke formation rate equals to the coke removal rate by supercritical hydrocarbon.     

Copolymerization of phenyl glycidyl ether with carbon dioxide catalyzed by ionic liquids

The copolymerization of phenyl glycidyl ether (PGE) and carbon dioxide was performed without any solvent in the presence of ionic liquid as catalyst. The reaction was carried out in a batch autoclave reactor. The carbonate content of polycarbonate was affected by the structure of imidazolium salt ionic liquid; the one with the cation of bulkier alkyl chain length and with more nucleophilic anion showed better reactivity. However, the yield of carbon dioxide addition decreased when hexyl or octyl containing ionic liquids were used in place of butyl group in 1-alkyl-3-methyl imidazolium salts. The carbonate content and turnover number (TON) of the polycarbonate increased as the reaction temperature increased from 40 to 80 ‡C. However, the carbonate content decreased with increasing reaction time.     

Lubricity-Enhancing Low-Temperature Diesel Fuel Additives

Branched chain alkyl esters have lower crystallization temperatures than those with straight chain headgroups. We investigated the effect of branched chain headgroups on the cold flow properties and lubricity of alkyl esters. Commercial grade canola methyl ester was transformed into branched chain alkyl esters through a two or three-stage base-catalyzed transesterification reaction with 1-methoxy-2-propanol and 3-methyl-1-butanol. Conversion rates between 85 and 95% were achieved. The alkyl esters exhibited improved cold flow properties. The pour points were reduced from −12 to −27 °C as a result of incorporating branched headgroups. Addition of 0.1 or 0.2% (v/v) 1-methoxy-2-propyl alkyl ester improved the lubricity of a commercial pre-production ultra low sulfur diesel (ULSD) fuel, as determined by increased lubricity number and reduced wear scar diameter. The inclusion of methyl-tert butyl ether or ethanolamides additives to ULSD containing alkyl esters had an antagonistic effect on lubricity. The branched-chain alkyl esters have the potential to be used as lubricity-enhancing and low-temperature fuel additives.     

Steam reforming of tar in hot syngas cleaning by different catalysts: Removal efficiency and coke layer characterization

Syngas produced by biomass and waste gasification processes must be adequately clean of tar compounds before being utilized in value-added applications. Syngas cleaning by tar cracking at high temperatures is a promising technique that can utilize different kinds of catalysts. However, their use is limited by the deposition of coke layers, which induces a masking phenomenon on the active surface, and, consequently, the rapid deactivation of the catalyst. This study addresses how the temperature (750 and 800°C) and the steam concentration (0% and 7.5%) can affect the extent of water–gas and reforming reactions between steam and coke deposits. Two catalysts were used: a market-available activated carbon and an iron-based alumina catalyst. The tests showed better performance of the Fe/γ-Al₂O₃ catalyst. A mass increase of the bed was measured in tests with both the catalysts, which confirms the deposition of the coke layer produced by tar dehydrogenation and carbonization. Scanning electronic microscopy-energy-dispersive X-ray analysis (SEM-EDX) and Raman spectroscopy were utilized to investigate the nature of coke layers over the catalyst surface, with the aim of acquiring information about their reactivity towards the water gas reaction. SEM-EDX observations indicate that the thickness of these carbon layers is less than 2 μm. Raman spectra suggest a negligible effect of the reaction temperature in the tested range and, in particular, that the amorphous nature of coke layers deposited in the presence of steam is relatively more graphitic than that obtained without steam.     

Modification of the Porosity of Pillared Clays by Carbon Deposition II. Hydrocarbon Cracking

To enhance the adsorption selectivity of pillared clays an attempt is made to modify the initial pore size by a controlled deposition of carbon. Cracking of hydrocarbons in the pores of the pillared clay results in coke deposits which can alter the pore size.Based on the evaluation of the amount of coke, the coke density, the decrease in micropore volume, changes in the micropore size distribution and the acidity it was possible to distinguish between pore-blocking, pore-filling and pore-narrowing effects.The modification mechanisms strongly depend on the initial porous structure, the acidity (Brönsted/Lewis), the cracking conditions (static or flow) and the hydrocarbons used.The carbon deposition results in a decrease in pore volume due to pore-filling (Ti-PILC) and pore-blocking (Al-PILC) without achieving a controlled pore-narrowing but some indications for pore-entrance narrowing were found.     

The influence of pitch-binder coke content on the properties and irradiation behavior of molded graphite

A series of needle-coke graphites were prepared with various fractions of pitch-binder coke in the range 5.5–14.2 wt-%. The specimens were irradiated to 9.70 × 10²¹n/cm² (E > 0.18 MeV) at 1225°C. Apparent bulk density and apparent crystallite size L_c were dependent on the binder-coke content. Crystallite orientation and thermal expansivities were not affected. Dimensional and volumetric changes were sensitive to binder-coke content; specimens deficient in binder-coke showed volumetric turnaround at lower fluences and higher expansion rates at high fluences. Specimens of 5.5 wt-% binder coke expanded 20 vol-%, whereas those of 11.7 wt-% binder coke expanded only 4 vol-%. Thermal expansivity increases closely followed the volume changes and were large in specimens deficient in binder coke. Unbonded coke particles expanded at three times the rate of coke particles bonded with pitch. The needle-coke particles were restrained by the binder coke during expansion at high fluences. Large cracks formed between filler particles during expansion and were responsible for the large volume expansions.     

On the determination of kinetic parameters for the regeneration of cracking catalyst

In the study of the regeneration of cracking catalyst, two approaches may be taken when determining the kinetic rate constant for the coke combustion reaction. A global coke burning rate equation may be considered, based on the observed oxygen concentration and carbon dioxide to carbon monoxide molar product ratio. This reaction may also be represented by an intrinsic coke burning equation which is a function of the oxygen concentration and the carbon dioxide to carbon monoxide molar ratio at the reaction site, combined with a carbon monoxide postcombustion equation. It is proposed in this paper that the rate constant for intrinsic coke burning, k^c, is essentially equal to the global coke burning rate constant, k_c, and that its value is independent of the rate equation chosen for the carbon monoxide post-combustion reaction.