Spent Fluid Catalytic Cracking Catalyst Research Articles

Reuse of spent FCC catalyst, waste serpentine and kiln rollers waste for synthesis of cordierite and cordierite-mullite ceramics

Spent fluid catalytic cracking (FCC) was gathered from several petrochemical plants and calcined in a rotary furnace between 1000 and 1100°C in order to remove sulphur and hydrocarbon based impurities. Calcining process on FCC led to formation of AlVO4 ceramic phase, so converted the hazardous waste to non-hazardous applicable raw material. In this study, two ceramic bodies as cordierite and cordierite-mullite were synthesized with calcined spent FCC, waste serpentine, kiln rollers waste and high grade kaolin as raw materials. The XRD results showed that the cordierite and cordierite-mullite were synthesized successfully so that 96.4% of F1 (cordierite) sample fired at 1400°C was cordierite phase and F2 (cordierite-mullite) sample fired at 1450°C was completely cordierite and mullite phases. The synthesized cordierite and cordierite-mullite samples had lower porosity values and coefficient of thermal expansion (CTE) than similar industrial products. The negative CTE value that obtained from the cordierite sample up to 800°C is favorable for some applications. The considerable results of the synthesized cordierite and cordierite-mullite from this work present cost reduction of the two ceramic bodies production and may help to solve the environmental problems with the use of three waste sources in large scales.

Recovery of rare earth elements from spent fluid catalytic cracking catalysts using leaching and solvent extraction techniques

This paper investigates the recovery of rare earth elements (REEs, mainly lanthanum and cerium) from spent fluid catalytic cracking (FCC) catalysts via the hydrometallurgical processes of leaching and liquid-to-liquid extraction. The maximum leaching efficiency (99.3% for REEs) was achieved under the following conditions: 2mol/L HCl, a solid-to-liquid (S/L) ratio of 1:10, leaching at 60°C for 2h, and 2h of roasting at 750°C prior to leaching. Because the main impurity element in the leachate was aluminum, the extractions of REEs and aluminum using di-2-ethylhexyl phosphoric acid (D2EHPA) and 2-ethylhexylphosphonic mono-2-ethylhexyl ester (HEHEHP) under different conditions were compared. The results indicated that D2EHPA and HEHEHP exhibited large extraction differences for REEs but small extraction capacity differences for aluminum. Based on the analysis of the experiments, the optimum extraction conditions for REEs were determined to be 0.5mol/L D2EHPA, equilibrium pH=2.5, ambient temperature and then stripping with 2mol/L HCl. The overall REEs recovery efficiency was 62.88%.

Vanadium-lithium alumina a potential additive for coke oxidation by CO2 in the presence of O2 during FCC catalyst regeneration

The possibility of performing the regeneration of spent fluid catalytic cracking catalysts in rich CO2 atmosphere can simultaneously reduce greenhouse gas emissions and produce CO for sequential uses. Herein alumina modified by vanadium and lithium was revealed a remarkable catalyst (or additive) for this goal. High CO2 conversion was observed in the presence of helium (for instance at 720 and 800°C, 39 and 76% of CO2 was converted during the first 5min of reaction respectively) and it was reduced by less than 5% in the presence of oxygen. Moreover the catalyst works effectively regardless the coke type on spent catalyst, i.e. produced by means of hydrocarbon or bio feed cracking. This catalyst was tested as an additive and works properly up to one part to ten of spent USY. By means of either labeled CO2 or coke (both with carbon 13) it was shown that primary 13CO2 forms 13CO followed by oxygen mobility between alumina and USY promoting coke oxidation. 12CO2 formed in-situ similarly to 13CO2 readily reacts with coke producing CO. These effects improve the coke burning by CO2 and remarkably increase the CO/CO2 ratio even in the presence of O2. Finally these results strongly support that the FCC regeneration step can be kept under auto-thermal condition in CO2 rich atmosphere.

High strength mortars using ordinary Portland cement–fly ash–fluid catalytic cracking catalyst residue ternary system (OPC/FA/FCC)

The use of ternary systems composed of ordinary Portland cement (OPC) and two pozzolanic mineral admixtures could supply several advantages in terms of the properties in both fresh and hardened states. Fly ash (FA) and spent fluid catalytic cracking catalyst (FCC) were combined to produce high strength mortars due to a synergic effect. OPC/FA systems (70%/30%) and OPC/FA/FCC systems (70%/20%/10%) were analyzed by thermogravimetric and SEM techniques. Mortars with different binder/sand ratios were prepared in order to yield high compressive strength values. On the one hand, fly ash particles act as nucleation sites that favour the hydration of Portland cement particles: at early stages (7days), the calculated fixed hydrated lime values were negative, suggestive of a nucleating effect. For a longer curing period (90days), the pozzolanic effect develops, as can be noted in terms of its compressive strength behaviour. The 90-days curing strength for OPC/FA mortars ranged between 96 and 98MPa. In ternary mixtures (OPC/FA/FCC), FCC act as pozzolan during the initial 7days period; the presence of fly ash particles favoured the presence of more portlandite by means of the nucleation effect. For longer curing times, fly ash particles also contribute to strength development, producing a synergic effect with FCC. The 90days curing strength for OPC/FA/FCC mortars ranged between 103 and 106MPa. Binary and ternary mortars reached strength activity index values equal or higher to the unit. Contributions to the strength (i.e. hydration of cement, the nucleation effect, and early and long term pozzolanic effects) have been calculated for 7 and 90 curing days pozzolan-containing mortars.

Resistencia a la corrosión ácida de morteros de cementos adicionados con catalizador de craqueo catalítico gastado (sFCC)

El catalizador de craqueo catalitico gastado (sFCC) es un residuo producido por la industria petroquimica y ha demostrado una elevada potencialidad como adicion puzolanica en mezclas de cemento Portland (OPC). El presente articulo evalua la eficacia del sFCC como adicion mineral activa en morteros de cemento Portland, asi como la resistencia al ataque quimico cuando los materiales producidos son inmersos en acido sulfurico (H2SO4), acetico (CH3COOH) o clorhidrico (HCl). Se llevo a cabo una comparacion del desempeno del sFCC como adicion frente a adiciones comercialmente disponibles, tales como humo de silice (SF) y metacaolin (MK). Los resultados revelan un incremento en las resistencias mecanicas de hasta un 17% en morteros con sFCC en comparacion a un mortero referencia sin adicion (OPC). La inmersion en H2SO4 durante 90 dias condujo a la formacion de yeso y perdida de resistencias mecanicas de hasta un ~25% en las mezclas con MK y sFCC. Para las muestras inmersas en HCl y especialmente las constituidas con sFCC y MK, se identifico Sal de Friedel, como consecuencia del ingreso de Cl- y posterior reaccion con los monosulfoaluminatos formados durante la hidratacion del cemento. La inmersion en acido acetico condujo a perdidas de resistencia de hasta un 57% para OPC y 37% para morteros adicionados con sFCC. De esta manera, la inmersion en HCl promueve el mayor ataque para los sistemas adicionados y posterior deterioro, seguido del CH3COOH y H2SO4. Se destaca el mejor desempeno del mortero con 20% sFCC, en particular en presencia de acido sulfurico. Rev. ing. constr. [online]. 2015, vol.30, n.3, pp. 169-176. ISSN 0718-5073. http://dx.doi.org/10.4067/S0718-50732015000300002

LDH-derived Ni catalyst as an effective catalyst in colophony hydrogenation and process optimization using response surface methodology

A natural biomass resin acid, colophony, was converted into a hydrogenated colophony over a nickel-based catalyst via catalytic hydrogenation in a 2 L stainless steel autoclave. This effective catalyst was derived from a layered double hydroxide precursor supported on spent fluid catalytic cracking catalyst, and the physicochemical properties of this catalyst were characterized by XRD, SEM, and H2-TPD techniques. The effects of temperature, pressure, and reaction time, and, in particular, interactions among process variables, on the conversion of abietic-type acids (AA, the main component of colophony) were investigated by response surface modeling through experimental Box–Behnken design. Results showed that temperature exerts the most significant effect on AA conversion and that nearly 100% AA conversion could be achieved at 178 °C, H2 pressure of 5.4 MPa, and reaction time of 94 mins. The experimental value of AA conversion was 99.73% under these conditions.

Kinetic study of the hydrogenation of a monoterpene over spent FCC catalyst‐supported nickel

A feasible route toward the sustainable synthesis of chemicals was provided via the transformation of monoterpene pinenes into pinane. This article discusses the conversion of pinenes to pinane over spent fluid catalytic cracking catalyst (SFCCC)‐supported nickel (Ni/SFCCC) at 110–130 °C and 2–6 MPa. The Ni/SFCCC catalyst was characterized by BET, XRD, SEM‐EDS, ICP, and FTIR. These measurements revealed that not only did the noble metal‐free catalyst Ni/SFCCC enhance the hydrogenation of pinenes to pinane, but a high cis‐trans ratio was also obtained: the conversion of pinenes and the cis‐trans ratio reached 98.48 % and 13.89, respectively. By fitting the kinetic data via the power‐law model, the hydrogenation of pinenes followed first‐order reaction kinetics, with the apparent activation energies for the hydrogenation of pinenes to cis‐ and trans‐pinane being 59.42 kJ/mol and 98.38 kJ/mol, respectively. The kinetic models described the formation of cis‐ and trans‐pinane well, with satisfactory accuracy compared to experimental observations. Furthermore, the reaction mechanism was derived via the Langmuir–Hinshelwood (L‐H) approach.

Synthesis of geopolymer from spent FCC: Effect of SiO<sub>2</sub>/Al<sub>2</sub>O<3 and Na2O/SiO2 molar ratios

This paper assesses the feasibility of using a spent fluid catalytic cracking catalyst (SFCC) as precursor for the production of geopolymers. The mechanical and structural characterization of alkali-activated SFCC binders formulated with different overall (activator + solid precursor) SiO2/Al2O3 and Na2O/SiO2 molar ratios are reported. Formation of an aluminosilicate ‘geopolymer’ gel is observed under all conditions of activation used, along with formation of zeolites. Increased SiO2/Al2O3 induces the formation of geopolymers with reduced mechanical strength, for all the Na2O/SiO2 ratios assessed, which is associated with excess silicate species supplied by the activator. This is least significant at increased alkalinity conditions (higher Na2O/SiO2 ratios), as larger extents of reaction of the spent catalyst are achieved. SiO2/Al2O3 and Na2O/SiO2 ratios of 2.4 and 0.25, respectively, promote the highest compressive strength (67 MPa). This study elucidates the great potential of using SFCC as precursor to produce sustainable ceramic-like materials via alkali-activation.

A novel “wastes-treat-wastes” technology: Role and potential of spent fluid catalytic cracking catalyst assisted ozonation of petrochemical wastewater

Catalytic ozonation is a promising wastewater treatment technology. However, the high cost of the catalyst hinders its application. A novel “wastes-treat-wastes” technology was developed to reuse spent fluid catalytic cracking catalysts (sFCCc) for the ozonation of petrochemical wastewater in this study. Multivalent vanadium (V4+ and V5+), iron (Fe2+ and Fe3+) and nickel (Ni2+) oxides that are distributed on the surface of sFCCc and poisoned FCC catalysts are the catalytic components for ozonation. The sFCCc assisted catalytic ozonation (sFCCc-O) of nitrobenzene indicated that the sFCCc significantly promoted hydroxyl radical mediated oxidation. The degradation rate constant of nitrobenzene in sFCCc-O (0.0794 min−1 at 298 K) was approximately doubled in comparison with that in single ozonation (0.0362 min−1 at 298 K). The sFCCc-O of petrochemical wastewater increased chemical oxygen demand removal efficiency by three-fold relative to single ozonation. The number of oxygen-containing (Ox) polar contaminants in the effluent (253) from sFCCc-O treatment decreased to about 70% of the initial wastewater (353). The increased oxygen/carbon atomic ratio and decreased number of Ox polar contaminants indicated a high degree of degradation. The present study showed the role and potential of sFCCc for catalytic ozonation of petrochemical wastewater, particularly in an advantage of the cost-effectiveness through “wastes-treat-wastes”.

Hydrogenation of pinene on spent fluid cracking catalyst supported nickel: Langmuir–Hinshelwood kinetic modelling

The kinetics for the pinene hydrogenation to pinane, the transformation of renewable biomass to useful chemicals, using spent fluid catalytic cracking catalyst (SFCC) supported nickel (Ni/SFCC), has been extensively investigated without any organic solvent, in the temperature range 373–393 K and the hydrogen pressure of 2–6 MPa in the absence of diffusional limitation. The non-noble metal catalyst was synthesized by incipient wet impregnation method and characterized by SEM, XPS and ICP. The catalytic effects of various parameters (catalyst weight, temperature and hydrogen pressure) on the reaction were reported, and the novel catalyst exhibited good activity. 17 kinds of Langmuir–Hinshelwood surface reaction mechanisms for the hydrogenation of pinene were proposed and derived. The best model described the experimental data with physically meaningful parameters was obtained by parameter diagnostics and a non-linear regression analysis, in which the surface reaction of adsorbed hydrogen atoms and pinene molecules over nickel catalyst was the rate-controlling step during the entire hydrogenation process. The activation energy of pinene surface hydrogenation to pinane was 118 ± 2.61 kJ mol−1 calculated from the Arrhenius plot.

The state of nickel in spent Fluid Catalytic Cracking catalysts

The speciation of Ni in spent Fluid Catalytic Cracking catalysts is studied. Carefully performed XRD analyses with NiO/SiO2 samples used as calibration standards, demonstrate that the presence of NiO as a separate phase is reliably detected also for NiO concentration close to 0.1 wt% (1000ppmw). Actually, both on real spent FCC catalysts (ECAT's) and on artificially contaminated industrial FCC catalysts, NiO is not detectable as a separate phase, even after contamination of the order of 15,000ppmw of Ni. SEM–EDS experiments provide evidence of a largely preferential location of Ni on alumina particles present in the FCC catalyst mixture, thus acting as “nickel traps”. XRD, UV–vis and TPR data confirm that Ni deposits on alumina particles forming a hardly reducible surface and subsurface layer, giving rise to a solid whose composition is NixAl2O3+x with x<<0.25. As a result of this, the formation of extended Ni metal particles in the raiser reactor is avoided, being their unwanted dehydrogenation activity essentially eliminated. The absence of bulk NiO in the spent FCC catalysts (at least when Ni content is in the range 2000–10,000ppmw) allows the classification of this material as a non-hazardous waste.

Corrosion Behavior of Steel Reinforcement in Concrete with Recycled Aggregates, Fly Ash and Spent Cracking Catalyst.

The main strategy to reduce the environmental impact of the concrete industry is to reuse the waste materials. This research has considered the combination of cement replacement by industrial by-products, and natural coarse aggregate substitution by recycled aggregate. The aim is to evaluate the behavior of concretes with a reduced impact on the environment by replacing a 50% of cement by industrial by-products (15% of spent fluid catalytic cracking catalyst and 35% of fly ash) and a 100% of natural coarse aggregate by recycled aggregate. The concretes prepared according to these considerations have been tested in terms of mechanical strengths and the protection offered against steel reinforcement corrosion under carbonation attack and chloride-contaminated environments. The proposed concrete combinations reduced the mechanical performance of concretes in terms of elastic modulus, compressive strength, and flexural strength. In addition, an increase in open porosity due to the presence of recycled aggregate was observed, which is coherent with the changes observed in mechanical tests. Regarding corrosion tests, no significant differences were observed in the case of the resistance of these types of concretes under a natural chloride attack. In the case of carbonation attack, although all concretes did not stand the highly aggressive conditions, those concretes with cement replacement behaved worse than Portland cement concretes.

Spent Fluid Catalytic Cracking Catalyst for Improving Early Strength of Portland Cement

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Geopolymers based on spent catalyst residue from a fluid catalytic cracking (FCC) process

This paper assesses the use of alkali activation technology in the valorization of a spent fluid catalytic cracking (FCC) catalyst, which is a residue derived from the oil-cracking process, to produce ‘geopolymer’ binders. In particular, the effects of activation conditions on the structural characteristics of the spent catalyst-based geopolymers are determined. The zeolitic phases present in the spent catalyst are the main phases participating in the geopolymerization reaction, which is driven by the conversion of the zeolitic material to a highly Al-substituted aluminosilicate binder gel. Higher alkali content and SiO2/Na2O ratio lead to a denser structure with a higher degree of geopolymer gel formation and increased degree of crosslinking, as identified through 29Si MAS NMR. These results highlight the feasibility of using spent FCC catalyst as a precursor for geopolymer production.

Chloride-induced corrosion behavior of reinforcing steel in spent fluid cracking catalyst modified mortars

Concrete properties can be improved by various additives. Nowadays there is a strong interest concerning the use of spent fluid catalytic cracking catalyst (SFCC) as an admixture to improve mechanical properties of concrete. This work aims at studying the corrosion resistance of steel rebars in SFCC modified mortar specimens. Results of physicochemical characterization indicate the acceleration of cement hydration due to pozzolanic activity of SFCC. Electrochemical measurements show that the addition of the SFCC enhances corrosion resistance by delaying its corrosion onset and decreasing the corrosion rate. These benefits can be attributed to the reduction of the mortar permeability.

Two-step pyrolysis of safflower oil cake

The thermal and catalytic pyrolysis of safflower oil cake was studied in a dual reactor system over catalyst; the first reactor containing no catalyst whereas the second reactor containing catalyst to upgrade the thermally cracked products. For comparison, pyrolysis experiments were also carried out in a single reactor system. The aim was to study the effect of catalyst and temperature on the product yields and composition of the bio-oil. The used catalysts are fluid catalytic cracking catalyst, red mud and activated red mud. The pyrolysis experiments were carried out at varying temperatures between 300 and 600°C in thermal reactor and 300–500°C in catalytic reactor. Although, the catalysts had no considerable effect on the yield of the pyrolysis product, they affected the bio-oil composition. It was very important observation that the amount of pyrolytic lignin compounds (11.8–27.5wt%) was significantly lower and extractives (50.0–65.1wt%) were higher in case of catalytic experiments. The H/Ceff ratio of bio-oils indicated that used catalysts had effective on deoxygenation. The gas chromatography–mass spectrometry analysis showed that the phenols were the dominant species in all bio-oils and their relative amounts, ranging from 26 to 35wt%, did not significantly changed with the pyrolysis conditions. The spent fluid catalytic cracking catalyst was successfully regenerated to achieve their original activity.

Pozzolanic activity of a spent fluid catalytic cracking catalyst residue

The reaction between a spent fluid cracking catalyst (FC3R) residue and portlandite was monitored over 56 days using several material characterisation techniques. The results showed that the residue was heterogeneous and composed of reactive and non-reactive fractions and that both fractions contained silicon and aluminium. After 56 days, the development of C–S–H gel was evident; part of the catalyst residue was pozzolanic. The CH combination could be monitored by thermogravimetry or X-ray diffraction, by measuring the signal corresponding to CH. However, due to the low crystallinity of cementing products and their complex stoichiometry, the above-mentioned techniques were less able to characterise C–A–S–H. However, nuclear magnetic resonance techniques allowed the evolution of the pozzolanic reaction to be evaluated and the hydrate products to be characterised.

Preparation of Ultrafine Y Zeolite from Spent Fluid Catalytic Cracking Catalyst Powders

Preparation of Ultrafine Y Zeolite from Spent Fluid Catalytic Cracking Catalyst Powders

Evaluation of electric properties of cement mortars containing pozzolans

In this paper the evolution of the microstructure of Portland cement mortar is analyzed, by using electrical impedance measurements. Cement mortars are compared without and with two pozzolanic substitutions: spent fluid catalytic cracking catalyst (FCC) and metakaolin (MK). The measurement method is described and the model for analyzing the electrical impedance spectra is developed. Three electrical parameters are defined: electrical resistivity, capacitance exponent, and capacitive factor. The results show a significant increase in resistivity of the mortars with pozzolans after 7 days of curing, especially in mortars with MK. This increase is correlated with lime-fixing by the pozzolans. The capacitive properties evolve differently at early age, but reach the same values after 148 days. The electrical and mineralogical data show that the evolution of the microstructure in the mortar with MK starts before it does in the mortars with FCC and that the final microstructure becomes different.

Study of attrition of Fe-based catalyst supported over spent FCC catalysts and their Fischer–Tropsch activity in a fixed bed reactor

Commercial spent fluid catalytic cracking (FCC) catalysts provided by Engelhard and Albemarle were used as supports for Fe-based catalysts with the goal of improving the attrition resistance of typical F–T catalysts. Catalysts with the Ruhrchemie composition (100Fe/5Cu/4.2K/25 spent FCC on mass basis) were prepared by wet impregnation. XRD and XANES analysis showed the presence of Fe 2O 3 in calcined catalysts. Fe x C and Fe 3O 4 were present in the activated catalysts. The metal composition of the catalysts was analyzed by ICP-MS. F–T activity of the catalysts activated in situ in CO at the same conditions as used prior to the attrition tests was measured using a fixed bed reactor at T = 573 K, P = 1.38 MPa and H 2:CO ratio of 0.67. Cu and K promoted Fe supported over Engelhard-spent FCC catalyst shows relatively high attrition resistance, CO conversion (81%) and C 5+ hydrocarbons selectivity (18.3%).