Degradation of LDPE/VGO mixtures to fuels using a FCC equilibrium catalyst in a sand fluidized bed reactor

Plastic degradation for recovery of useful products or raw materials is a very interesting alternative for reducing the plastic accumulation. This paper explores the possibility of using refinery facilities to carry out the plastic cracking as well as to take the most of the products obtained. In the present work, LDPE/VGO blends with different percentages of polymer are degraded in presence of a FCC equilibrium catalyst. The reactor used in this study is a laboratory scale sand fluidized bed reactor at 500 °C, and a 7:1 catalyst:LDPE/VGO blend ratio in order to simulate the operating conditions in a large scale industrial reactor. Polyethylene blends evaluated show relative proportions of LDPE of 0, 6, 25, 75 and 100% (w/w). Gas and liquid compounds were collected and quantified. The results obtained are compared with those generated in a thermal cracking.

In all cases, the FCC equilibrium catalyst showed a high selectivity to the production of isobutane and isopentane in the volatile compounds as well as to aromatics in the liquid products.

Results shown in this paper evidences the viability of introducing plastics into FCC unit, producing potential valuable products from low value materials.     

Catalytic conversion of commingled polymer waste into chemicals and fuels over spent FCC commercial catalyst in a fluidised-bed reactor

A commingled post-consumer polymer (CPW#1) was pyrolysed over spent fluid catalytic cracking (FCC) commercial catalyst (ECat-1) using a laboratory fluidised-bed reactor operating isothermally at ambient pressure. The influence of reaction conditions including catalyst, temperature, ratios of commingled polymer to catalyst feed and flow rates of fluidising gas was examined. The conversion for spent FCC commercial catalyst (82.7 wt%) gave much higher yield than silicate (only 14.2 wt%) and the highest yield (nearly 87 wt%) was obtained for ZSM-5. Greater product selectivity was observed with ECat-1 as a recycled catalyst with about 56 wt% olefins products in the C₃–C₇ range. The selectivity could be further influenced by changes in reaction conditions. Valuable hydrocarbons of olefins and iso-olefins were produced by low temperatures and short contact times used in this study. It is also demonstrated that the use of spent FCC commercial catalyst and under appropriate reaction conditions can have the ability to control both the product yield and product distribution from polymer degradation, potentially leading to a cheaper process with more valuable products.     

Catalytic degradation of waste polyolefinic polymers using spent FCC catalyst with various experimental variables

Liquid-phase catalytic degradation of waste polyolefinic polymers (HDPE, LDPE, PP) over spent fluid catalytic cracking (FCC) catalyst was carried out at atmospheric pressure with a stirred semi-batch operation. The effect of experimental variables, such as catalyst amount, reaction temperature, plastic types and weight ratio of mixed plastic on the yield and accumulative amount distribution of liquid product for catalytic degradation was investigated. The initial rate of catalytic degradation of waste HDPE was linearly increased with catalyst amount (4-12 wt%), while that was exponentially increased with reaction temperature (350-430 ‡C). Spent FCC catalyst in the liquid-phase catalytic degradation of polymer was not deactivated fast. The product distribution from catalytic degradation using spent FCC catalyst strongly depended on the plastic type. The catalytic degradation of mixed plastic (HDPE: LDPE: PP: PS=3: 2: 3: 1) showed lower degradation temperature by about 20 ‡C than that of pure HDPE.     

Study of the accessibility effect on the irreversible deactivation of FCC catalysts from contaminant feed metals

Two commercial FCC catalysts were investigated to explore the effect of their different accessibility on the catalyst activity, selectivity and deactivation due to deleterious feed metals (V and Ni). Feed metal Fe was not included in the present study. E-Cats (equilibrium samples from a commercial FCC unit) of both FCC catalysts and the corresponding laboratory-deactivated samples (applying the cyclic deactivation (CD) and the cyclic propylene steaming (CPS) methods) were thoroughly studied. Extensive characterization (XRD, N₂ physisorption, measurement of Akzo Accessibility Index (AAI), SEM-EDS analysis) of all samples was realized to investigate variations in their crucial properties due to metal deposition. Comparison of E-Cats, CD and CPS samples revealed a very different nickel deposition profile over the CPS samples. In all cases, V was homogenously distributed throughout the particle, as expected due to its mobility. Ni–Al mixed phases, observed on the E-Cat samples, were probably formed during ageing and are expected to be inactive. The absence of such phases on the laboratory-deactivated samples can be attributed both to the inability of the two deactivation methods to simulate metal ageing during commercial utilization of the FCC catalyst and the absence of Fe incorporation during laboratory deactivation. All catalytic samples (E-Cats and artificially deactivated FCC catalysts) were evaluated in the laboratory using two bench-scale Microactivity Test (MAT) units of different reactor configuration: fixed-bed (SCT-MAT unit) and fluid-bed (AUTOMAT unit). Similar ranking of the catalysts is achieved when using both units. However, AUTOMAT unit seems to provide a clearer diversification of catalysts with different accessibility. Both laboratory deactivation methods seem to be rather inefficient in simulating the real deactivation, since they are always exaggerating metal effects.     

Thermochemical conversion of polymer wastes into hydrocarbon fuels over various fluidizing cracking catalysts

A mixture of hospital post-commercial polymer waste (LDPE/HDPE/PP/PS) was pyrolyzed over various catalysts using a fluidized-bed reactor operating isothermally at ambient pressure. The yield of volatile hydrocarbons with zeolitic catalysts (ZSM-5 > MOR > USY) were higher than with non-zeolitic catalysts (MCM-41 > ASA). MCM-41 with large mesopores and ASA with weaker acid sites resulted in a highly olefinic product mixture with a wide carbon number distribution, whereas USY yielded a saturate-rich product mixture with a wide carbon number distribution and substantial coke levels. The systematic experiments discussed in this paper show that the use of various catalysts improves the yield of hydrocarbon products and provide better selectivity in the product distributions. A novel developed model based on kinetic and mechanistic considerations which take into account chemical reactions and catalyst deactivation for the catalytic degradation of commingled polymer waste has been investigated. This model represents the benefits of product selectivity for the chemical composition such as alkanes, alkenes, aromatics and coke in relation to the performance and the particle size selection of the catalyst used as well as the effect of the fluidizing gas and reaction temperature.     

Development of Ni catalysts for gas production from biomass gasification. Reactivity in steam- and dry-reforming

Biomass gasification can be optimised in a fluidised bed by the use of metallic nickel as active phase grafted on olivine. Natural olivine ((Mg, Fe)₂SiO₄) has been chosen as catalyst support because of its activity in biomass steam gasification and tar cracking, its high attrition resistance.

After impregnation of nickel oxide on olivine and calcination at 900, 1100 or 1400°C, different interactions between the precursor and the support have been revealed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy coupled to energy dispersive X-ray spectroscopy. Temperature programmed reduction has completed this study and permitted to control the reducibility of the catalysts. The most promising catalyst determined after these different characterisation studies contained 2.8 wt.% of Ni and was calcined at 1100°C. It exhibited strong nickel–olivine interaction but the grafted nickel oxide particles stayed reducible under catalytic test conditions.

Already at 750°C, this catalyst presented a high activity in dry-reforming (95% methane conversion) and steam-reforming (88% methane conversion) and yield in syngas (80% and 75% CO yield, respectively). An excess of water content in steam-reforming inhibited the catalytic activation which could be retrieved by addition of a reducer like H₂.

No sintering of nickel particles and very little carbon deposition has been observed on this catalytic system by characterisation studies after catalytic tests. This can explain its very good ageing behaviour (at least 260 h at 800°C) and justifies its use in a fluidised bed pilot plant.     

Recycling polystyrene into fuels by means of FCC: performance of various acidic catalysts

In accordance with the option of recycling plastics into fuels by dissolving them in standard feedstocks for the process of catalytic cracking of hydrocarbons, FCC, various acidic catalysts (zeolites ZSM-5, mordenite, Y, and a sulfur-promoted zirconia) were tested in the conversion of polystyrene dissolved into inert benzene at 550°C in a fluidized-bed batch reactor. Experiments were performed with very short contact times of up to 12 s. Main products were in the gasoline range, including benzene, toluene, ethylbenzene, styrene, and minor amounts of C_9–12 aromatics and light C₅₋ compounds. Coke was always produced in very significant amounts. All the products can be justified with basis on the properties of each catalyst and the various possible catalytic reaction pathways: cracking after protolytic attack on the polymer fragments, styrene oligomerization and subsequent cracking, or hydrogen transfer to styrene. Styrene would be mainly produced in this system from thermal cracking of the polymer as the initial step. If present, shape selectivity effects due to catalyst structure can influence significantly the prevalence of the various reactions, because they would interfere with those undergoing bulky transition states, like styrene oligomerization or hydrogen transfer. Even though sulfur-promoted zirconia is highly acidic, the low proportion of Brønsted-type acid sites does not allow the occurrence of secondary styrene reactions. It was shown that most favorable product distributions (higher yields of desirable products) are obtained on equilibrium commercial FCC catalysts.     

Fluid catalytic cracking feed hydrotreatment and its severity impact on product yields and quality

This paper investigates the effect of fluid catalytic cracking (FCC) feed hydrotreatment and its severity increase on product yields and quality obtained in a commercial and a laboratory MAT FCC units. The hydrotreatment of Ural heavy vacuum gas oil reduces not only sulfur, nitrogen, Conradson carbon and metals content in the FCC feed but also increases the mononuclear aromatic hydrocarbons content by 8% absolute at almost no change in the total aromatics content. Regardless of this 8% increase of the mononuclear aromatics in the hydrotreated FCC feed the conversion increase in both commercial and laboratory MAT units was only 2%. The severity increase in the FCC feed hydrotreater leads to a higher conversion in the FCC, higher hydrogen transfer rate that results in higher isobutane/butylenes ratio, lower gasoline olefins content, and higher gasoline motor octane number. The hydrotreatment of the Ural heavy vacuum gas oil exhibited the same changes in FCC catalyst selectivities: lower coke and LCO selectivities and higher gasoline selectivity in both commercial riser FCC unit that has between 2 and 3 s time on stream, and the fixed bed reactor MAT unit, that has 30 s time on stream.     

DOC-Ⅰ降烯烃催化剂小型提升管反应性能评价

采用小型提升管催化裂化试验装置评价研制的DOC-Ⅰ降烯烃催化剂的催化裂化反应性能。结果表明,在反应温度500 ℃、剂油质量比6和停留时间1.99 s条件下,DOC-Ⅰ催化剂上原料油的转化率达75.01%,较参比催化剂提高1.79个百分点,相应的液化气产率降低0.28个百分点,汽油产率增加2.9个百分点,烯烃含量下降5.21个百分点,异构烷烃和芳烃含量明显增加,产品分布有效改善。表明研制的DOC-Ⅰ催化剂具有较好的催化裂化性能和降烯烃能力。     

The catalytic oxidative coupling of methane: II. Axial gas sample probing in a bubbling Fluidised-Bed reactor and the effect of side reactions

The atmospheric pressure catalytic oxidative coupling of methane was studied in detail by axial gas concentration probing experiments in a 60 mm OD bubbling fluidised-bed reactor system. Experimental data demonstrated a very fast reaction which occurred within the vicinity of the distributor (normally in the first 5 mm of bed height) under normal reaction conditions of 850°C and 83 vol%/17 vol% CH₄/O₂ feed. The data also showed that hydrocarbon selectivity was deleteriously affected by side reactions which were also promoted by the catalysts even though they were good catalysts for the oxidative coupling reaction. If this reduction in hydrocarbon selectivity is inevitable then there will be optimum operating conditions for each catalyst in the bubbling fluidised bed reactor.     

Activity and product distribution of alumina supported platinum and palladium catalysts in the gas-phase oxidative decomposition of chlorinated hydrocarbons

The complete catalytic oxidation of 1,2-dichloroethane (DCE) and trichloroethylene (TCE) over alumina supported noble metal catalysts (Pt and Pd) was evaluated. Experiments were performed at conditions of lean hydrocarbon concentration (around 1000 ppm) in air, between 250°C and 550°C in a conventional fixed bed reactor. The catalysts were prepared in a range of metal contents from 0.1 to 1 wt%. Palladium catalysts resulted to be more active than platinum catalysts in the oxidation of both chlorinated volatile organic compounds. DCE was completely destructed at 375°C, whereas TCE required 550°C. HCl was the only chlorine-containing product in the oxidation of DCE in the range of 250–400°C. Tetrachloroethylene was observed as an intermediate in the oxidation of TCE, being formed to a significant extent between 400°C and 525°C. CO was also detected in the oxidation of both DCE and TCE over Pd catalysts, though at temperatures of complete destruction, CO₂ was the only carbon-containing product. The Pt catalysts were selective to CO₂ at the studied conditions.     

Two-stage cracking catalyst of amorphous silica-alumina on Y zeolite for enhanced product selectivity and suppressed coking

A novel bilayer catalyst composed of amorphous silica-alumina (ASA) layer coated on Y zeolite layer is proposed as a fluid catalytic cracking (FCC) catalyst to cause two-stage reactions of pre-cracking and deep-cracking. The bilayer catalyst (Y/ASA) is compared with the usual mixed one (ASA+Y), in catalytic cracking of a feed composed of 1,3,5-triisopropylbenzene and naphthalene. The two catalyst representations were prepared by applying layers of Y zeolite and ASA or both on inert monolith supports. Catalytic cracking experiments were carried out at 300, 350 and 400 °C. Compared to Y+ASA, Y/ASA yielded about 33% and 46% more benzene and toluene, respectively, and 18% less coke in the catalytic cracking at 350 oC. The coke of Y/ASA was less refractory than that of Y+ASA as burnt at lower temperatures, while emitting less carbon monoxide in regeneration. Y/ASA configuration shows promising features as FCC catalysts for increased bottoms cracking and suppressed coking.     

A comparative study of liquid product on non-catalytic and catalytic degradation of waste plastics using spent FCC catalyst

Non-catalytic and catalytic degradation of waste plastics (high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS)) using spent fluid catalytic cracking (FCC) catalyst into liquid product were comparatively studied with a stirred semi-batch reactor at 400 ‡C, under nitrogen stream. Liquid product characteristics were described by cumulative distribution as a function of lapse time of reaction, paraffin, olefin, naphthene and aromatic (PONA) composition, and also carbon number distribution on plastic type of reactant. For degradation of waste PE with relatively high degradation temperature, the effect of adding spent FCC catalyst greatly appeared on cumulative distribution of liquid product with a reaction lapse time, whereas those for waste PP and PS with low degradation temperature showed a similar trend in both non-catalytic and catalytic degradation at 400 ‡C. In PONA and carbon number distribution of liquid product, the characteristics of waste PS that was mainly degraded by end chain scission mechanism were not much altered in presence of spent FCC catalyst. However, waste polyolefinic polymer that was degraded by a random chain scission mechanism significantly differed on PONA and carbon number distribution of liquid product with or without spent FCC catalyst. The addition of spent FCC catalyst in degradation of polyolefinic polymer, which economically has a benefit in utilization of waste catalyst, significantly improved the light olefin product by its high cracking ability and also the aromatic product by cyclization of olefin as shape selectivity in micropore of catalyst.     

Dependence of Fluid Catalytic Cracking Unit Performance on H-Oil Severity,Catalyst Activity,and Coke Selectivity

The effect of the quality of ebullated bed vacuum residue H-Oil hydrocracking gas oils cracked in a commercial fluid catalytic cracking unit (FCCU) on its performance was studied. Six different catalysts were employed in this study. Four catalysts were tested in a commercial FCCU, and two in a laboratory FCCU. An increase of the H-Oil hydrocracker reaction temperature was associated with a decrease in the K_W factor of the H-Oil gas oils. The diminished K_W factor of H-Oil gas oils resulted in lower FCCU conversion and higher regenerator temperatures. The FCC conversion at maximum gasoline yield is best predicted by the feed K_W factor. The higher-activity, higher-Δcoke catalyst is unfavorable for FCCU performance because the excessive regenerator temperature excursions require reduction of the throughput.     

Feedstock recycling of agriculture plastic film wastes by catalytic cracking

Feedstock recycling by catalytic cracking of a real plastic film waste from Almeria greenhouses (Spain) towards valuable hydrocarbon mixtures has been studied over several acid catalysts. The plastic film waste was mostly made up of ambient degraded low-density polyethylene (LDPE) and ethylene-vinyl acetate (EVA) copolymer, the vinyl acetate content being around 4 wt.%. Nanocrystalline HZSM-5 zeolite (crystal size 60 nm) was the only catalyst capable of degrading completely the refuse at 420 °C despite using a very small amount of catalyst (plastic/catalyst mass ratio of 50). However, mesoporous catalysts (Al-SBA-15 and Al-MCM-41), unlike it occurred with virgin LDPE, showed fairly close conversions to that of thermal cracking. Nanocrystalline HZSM-5 zeolite led to 60 wt.% selectivity towards C₁---C₅ hydrocarbons, mostly valuable C₃---C₅ olefins, what would improve the profitability of a future industrial recycling process. The remarkable performance of nanocrystalline HZSM-5 zeolite was ascribed to its high content of strong external acid sites due to its nanometer dimension, which are very active for the cracking of bulky macromolecules. Hence, nanocrystalline HZSM-5 can be regarded as a promising catalyst for a feasible feedstock recycling process by catalytic cracking.     

催化、动力学与反应器Pt/Y催化剂催化FCC柴油加氢制备BTX

利用Pt/Y催化剂,在固定床反应器中,温度380℃、压力3 MPa、氢油体积比1000及质量空速1.0 h^-1条件下,分别采用加氢处理的全馏分和轻馏分催柴为原料制备苯、甲苯和二甲苯（BTX）,获得（C₆+C₇+C₈）芳烃的总选择性分别为9.4%和33.9%。对原料和液体产物进行的气相色谱和质谱分析表明,BTX主要经过重芳烃的加氢饱和、裂解等反应生成,中间物质为烷基苯、四氢萘、茚满及茚类等单环芳烃。通过对反应原料以及对反应前后催化剂的N₂吸脱附、NH₃-TPD、XRD衍射图谱、TG等物化性质的表征,分析催化剂失活的主要原因。即全馏分催柴原料中高含量的S、N化合物快速吸附造成了催化剂中毒,而轻馏分原料中S、N化合物在催化剂表面的缓慢积累覆盖活性位,造成催化剂逐渐失活。     

Effects of metal modifications of Y zeolites on sulfur reduction performance in fluid catalytic cracking process

The acidity of catalytically active component, e.g., ultra stable Y zeolite (USY), plays an important role in determining their cracking activity and selectivity. To develop advanced sulfur reduction catalytic cracking catalysts, different type of elements were used to modify USY and the resulting catalysts were evaluated in a confined fluidized bed reactor and a micro-activity testing unit. The relation between the acidity of the zeolite and the conversion of sulfur compounds as well as the distributions of fluid catalytic cracking (FCC) products were discussed. The results showed that the rare earth (RE) metal can stabilize the catalyst and increase the conversion, but cannot increase the selectivity to thiophene compounds; V can reduce the sulfur content by 36.3 m%, but decreases the overall conversion compared with the base catalyst. An optimum catalyst was obtained by the combined RE and V modification, over which the sulfur content in FCC gasoline can be decreased and the selectivity for the target products can be improved, with the sulfur content reduced by 30 m% and the selectivity to coke even decreased by 0.20 m% at a comparable conversion level of the base catalyst.     

Experimental comparison of biomass chars with other catalysts for tar reduction

In this paper the potential of using biomass char as a catalyst for tar reduction is discussed. Biomass char is compared with other known catalysts used for tar conversion. Model tar compounds, phenol and naphthalene, were used to test char and other catalysts. Tests were carried out in a fixed bed tubular reactor at a temperature range of 700–900 °C under atmospheric pressure and a gas residence time in the empty catalyst bed of 0.3 s. Biomass chars are compared with calcined dolomite, olivine, used fluid catalytic cracking (FCC) catalyst, biomass ash and commercial nickel catalyst. The conversion of naphthalene and phenol over these catalysts was carried out in the atmosphere of CO₂ and steam. At 900 °C, the conversion of phenol was dominated by thermal cracking whereas naphthalene conversion was dominated by catalytic conversion. Biomass chars gave the highest naphthalene conversion among the low cost catalysts used for tar removal. Further, biomass char is produced continuously during the gasification process, while the other catalysts undergo deactivation. A simple first order kinetic model is used to describe the naphthalene conversion with biomass char.     

Conversion of waste plastics into fuels: Recycling polyethylene in FCC

Low density polyethylene was dissolved into toluene and converted at 500 °C over three different commercial FCC catalysts in a laboratory Riser Simulator reactor. Short reaction-times up to 12 s were used. All the catalysts had qualitatively similar behaviors. The specific contribution of the polymer to the product slate of FCC was centered in hydrocarbons in the range of gasoline, with high aromatic content and highly olefinic C₃–C₄ gases. Saturated C₄–C₅ products were mainly isoparaffins. The additional coke formed by the polymer would make coke yields to increase moderately in relation to the standard operation. These facts confirmed that this recycling option, which is based on a proven technology, represents an interesting alternative to solve a major environmental problem.     

A novel fluid catalytic cracking approach for producing low aromatic LCO

Four FCC catalysts were compared in a CREC Riser Simulator reactor using an aromatic Brazilian VGO feed aiming at maximum low aromatic middle distillate production. Differences in activity were compensated by changes in the contact time. The first catalyst (A) was a maximum LCO commercial grade, the other three being experimental catalysts, including a pair of related materials in which one of the catalysts (M2) was produced by modulating the acidity of the other one (M1). Inert non porous silica was evaluated as a thermal cracking reference. The four catalysts were characterized as tested using temperature-programmed desorption of n-propylamine to determine their Brönsted acidity. The commercial catalyst A was by far the most acidic catalyst, followed by catalyst M1. Brönsted acidity of the two other catalysts M2 and B was about one tenth the value of catalyst A. Lowering the Brönsted acidity reduced catalyst activity, but it was possible to recover conversion by increasing reaction time, which was not the case with the thermal cracking reference. The yields of light naphtha and of aromatic hydrocarbons in the C10 and C11 range (inversely correlated to LCO Cetane) of the low acidity catalysts B and M2 was reduced by 30% and 50% respectively and LCO (C12 to C20 hydrocarbons) was increased by 33%, compared to catalyst A at the same slurry oil yield.