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Keywords = butene cracking

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19 pages, 3246 KiB  
Article
Direct Conversion of 1,3-Butanediol to 1,3-Butadiene over ZSM-22 Catalysts: Influence of the Si/Al Ratio
by Loïc Eloi, Jeroen Poissonnier, Arne De Landsheere, Dhanjay Sharma, Jaouad Al Atrach, Valérie Ruaux, Valentin Valtchev, Maarten K. Sabbe, Joris W. Thybaut and An Verberckmoes
Catalysts 2025, 15(7), 655; https://doi.org/10.3390/catal15070655 - 5 Jul 2025
Viewed by 553
Abstract
ZSM-22 zeolites with different Si/Al ratios (38, 50, 80) were prepared via a hydrothermal synthesis method, investigated for the catalytic dehydration of 1,3-butanediol (1,3-BDO) to butadiene (BD) at 300 °C. The catalytic performance of the synthesized materials was related to their properties and [...] Read more.
ZSM-22 zeolites with different Si/Al ratios (38, 50, 80) were prepared via a hydrothermal synthesis method, investigated for the catalytic dehydration of 1,3-butanediol (1,3-BDO) to butadiene (BD) at 300 °C. The catalytic performance of the synthesized materials was related to their properties and compared to a commercial ZSM-22 zeolite (Si/Al = 30). ZSM-22 (50) exhibited a quick decline in conversion, a lower BD selectivity, and higher propylene selectivity compared to the other materials, which could be attributed to the presence of strong Lewis acid sites and silanol nests. The Lewis sites favor the cracking of the intermediate 3-buten-1-ol (3B1OL) into propylene, while the silanol nests interact with the free hydroxyl group of 3B1OL, potentially inhibiting further dehydration towards BD. The highest initial BD yield of 74% was observed over ZSM-22 (80), while the highest initial BD productivity of 2.7 gBD·g−1cata·h−1 was achieved over ZSM-22 (38). After 22 h time on stream (TOS), c-ZSM-22 and ZSM-22 (38) outperformed previously reported catalysts from the literature, with productivities amounting to 1.3 gBD·g−1cata·h−1 and 1.2 gBD·g−1cata·h−1, respectively, at a site time of 6.6 molH+·s·mol−11,3-BDO. Full article
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17 pages, 9926 KiB  
Article
Enhanced Stability and Selectivity in Pt@MFI Catalysts for n-Butane Dehydrogenation: The Crucial Role of Sn Promoter
by Nengfeng Gong, Gaolei Qin, Pengfei Li, Xiangjie Zhang, Yan Chen, Yong Yang and Peng He
Catalysts 2024, 14(11), 760; https://doi.org/10.3390/catal14110760 - 29 Oct 2024
Cited by 5 | Viewed by 1790
Abstract
The dehydrogenation of n-butane to butenes is a crucial process for producing valuable petrochemical intermediates. This study explores the role of oxyphilic metal promoters (Sn, Zn, and Ga) in enhancing the performance and stability of Pt@MFI catalysts for n-butane dehydrogenation. The [...] Read more.
The dehydrogenation of n-butane to butenes is a crucial process for producing valuable petrochemical intermediates. This study explores the role of oxyphilic metal promoters (Sn, Zn, and Ga) in enhancing the performance and stability of Pt@MFI catalysts for n-butane dehydrogenation. The presence of Sn in the catalyst inhibits the agglomeration of Pt clusters, maintaining their subnanometric particle size. PtSn@MFI exhibits superior stability and selectivity for butenes while suppressing cracking reactions, with selectivity for C1–C3 products as low as 2.1% at 550 °C compared to over 30.5% for Pt@MFI. Using a combination of high-angle annular dark-field scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy, we examined the structural and electronic properties of the catalysts. Our findings reveal that Zn tends to consume hydroxyl groups and substitute framework sites, and Ga induces more defective sites in the zeolite structure. In contrast, the interaction between SnOx and the zeolite framework does not depend on reactions with hydroxyl groups. The incorporation of Sn significantly prevents Pt particle agglomeration, maintaining smaller Pt particle sizes and reducing coke formation compared to Zn and Ga promoters. Theoretical calculations showed that Sn increases the positive charge on Pt clusters, enhancing their interaction with the zeolite framework and reducing sintering, albeit with a slight increase in the energy barrier for C-H activation. These results underscore the dual benefits of Sn as a promoter, offering enhanced structural stability and reduced coke formation, thus paving the way for the rational design of more effective and durable catalysts for alkane dehydrogenation and other high-value chemical processes. Full article
(This article belongs to the Section Nanostructured Catalysts)
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21 pages, 2438 KiB  
Review
A Review of Catalyst Modification and Process Factors in the Production of Light Olefins from Direct Crude Oil Catalytic Cracking
by Ruth Eniyepade Emberru, Raj Patel, Iqbal Mohammed Mujtaba and Yakubu Mandafiya John
Sci 2024, 6(1), 11; https://doi.org/10.3390/sci6010011 - 4 Feb 2024
Cited by 7 | Viewed by 6614
Abstract
Petrochemical feedstocks are experiencing a fast growth in demand, which will further expand their market in the coming years. This is due to an increase in the demand for petrochemical-based materials that are used in households, hospitals, transportation, electronics, and telecommunications. Consequently, petrochemical [...] Read more.
Petrochemical feedstocks are experiencing a fast growth in demand, which will further expand their market in the coming years. This is due to an increase in the demand for petrochemical-based materials that are used in households, hospitals, transportation, electronics, and telecommunications. Consequently, petrochemical industries rely heavily on olefins, namely propylene, ethylene, and butene, as fundamental components for their manufacturing processes. Presently, there is a growing interest among refineries in prioritising their operations towards the production of fuels, specifically gasoline, diesel, and light olefins. The cost-effectiveness and availability of petrochemical primary feedstocks, such as propylene and butene, can be enhanced through the direct conversion of crude oil into light olefins using fluid catalytic cracking (FCC). To achieve this objective, the FCC technology, process optimisation, and catalyst modifications may need to be redesigned. It is helpful to know that there are several documented methods of modifying traditional FCC catalysts’ physicochemical characteristics to enhance their selectivity toward light olefins’ production, since the direct cracking of crude oil to olefins is still in its infancy. Based on a review of the existing zeolite catalysts, this work focuses on the factors that need to be optimized and the approaches to modifying FCC catalysts to maximize light olefin production from crude oil conversion via FCC. Several viewpoints have been combined as a result of this research, and recommendations have been made for future work in the areas of optimising the yield of light olefins by engineering the pore structure of zeolite catalysts, reducing deactivation by adding dopants, and conducting technoeconomic analyses of direct crude oil cracking to produce light olefins. Full article
(This article belongs to the Section Chemistry Science)
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14 pages, 2539 KiB  
Article
Catalytic Cracking of Fischer-Tropsch Wax on Different Zeolite Catalysts
by Chao Yang, Lingtao Liu, Genquan Zhu, Chaogang Xie, Xiance Zhang and Xiaoqiao Zhang
Catalysts 2023, 13(8), 1223; https://doi.org/10.3390/catal13081223 - 18 Aug 2023
Cited by 3 | Viewed by 3077
Abstract
Fisher-Tropsch synthesis (FTS) is a promising method to make alternative hydrocarbons from biomass or other resources. Upgrading the primary FTS products is of considerable interest. Cracking FT wax is economically attractive to produce light olefins. Herein, the effects of the zeolite type, Si/Al [...] Read more.
Fisher-Tropsch synthesis (FTS) is a promising method to make alternative hydrocarbons from biomass or other resources. Upgrading the primary FTS products is of considerable interest. Cracking FT wax is economically attractive to produce light olefins. Herein, the effects of the zeolite type, Si/Al ratio of ZSM-5, and reaction condition on the catalytic cracking of FT wax were investigated. It was found that the pore structure and acid properties of zeolites had a significant impact on the product selectivity. USY was beneficial for the production of gasoline and diesel, while β was suitable for the production of propylene and butenes, and ZSM-5 was conductive to producing ethylene and propylene. Increasing the Si/Al ratio of ZSM-5 can suppress the hydrogen transfer reaction and increase the selectivity of light olefins. When the Si/Al ratio of ZSM-5 was 140, the mass yields of ethylene, propylene, and butenes were 6.40%, 26.83%, and 20.10%, respectively. Full article
(This article belongs to the Special Issue Zeolites and Zeolite-Based Catalysts in Industrial Catalysis)
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12 pages, 3902 KiB  
Article
Effect of Molecular Structure of C10 Hydrocarbons on Production of Light Olefins in Catalytic Cracking
by Lingyin Du, Yueyang Han and Youhao Xu
Catalysts 2023, 13(6), 1013; https://doi.org/10.3390/catal13061013 - 16 Jun 2023
Cited by 5 | Viewed by 2782
Abstract
The effect of the molecular structure of feedstock on the cracking reaction of C10 hydrocarbons to ethylene and propylene over H-ZSM-5 zeolite was investigated. To better compare the effect of decane on the production of light olefins, the thermal cracking and catalytic cracking [...] Read more.
The effect of the molecular structure of feedstock on the cracking reaction of C10 hydrocarbons to ethylene and propylene over H-ZSM-5 zeolite was investigated. To better compare the effect of decane on the production of light olefins, the thermal cracking and catalytic cracking performance of decane were first investigated. As a comparison, the thermal cracking and catalytic cracking of decane were studied by cracking over quartz sand and H-ZSM-5. Compared with the thermal cracking reaction over quartz sand, the catalytic cracking reaction of decane over H-ZSM-5 has a significantly higher conversion and light olefins selectivity, especially when the reaction temperature was lower than 600 °C. On this basis, the catalytic cracking reactions of decane and decene over H-ZSM-5 were further compared. It was found that decene with a double bond structure had high reactivity over H-ZSM-5 and was almost completely converted, and the product was mainly olefin. Compared with decane as feedstock, it has a lower methane yield and higher selectivity of light olefins. Therefore, decene was more suitable for the production of light olefins than decane. To this end, we designed a new light olefin production process. Through olefin cracking, the yield of light olefins in the product can be effectively improved, and the proportion of different light olefins such as ethylene, propylene and butene can be flexibly adjusted. Full article
(This article belongs to the Special Issue Catalytic Conversion of Low Carbon Alkane)
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15 pages, 2033 KiB  
Article
Optimization and Control of Propylene Production by Metathesis of 2-Butene
by Andrei Maxim Andrei and Costin Sorin Bildea
Processes 2023, 11(5), 1325; https://doi.org/10.3390/pr11051325 - 25 Apr 2023
Cited by 3 | Viewed by 3654
Abstract
This article considers the design and control of the 2-butene metathesis process. The process transforms a low-value feedstock derived from a fluid catalytic cracking unit into more valuable products. The economical optimization is applied to the preheat–reaction and separation sections, with the objective [...] Read more.
This article considers the design and control of the 2-butene metathesis process. The process transforms a low-value feedstock derived from a fluid catalytic cracking unit into more valuable products. The economical optimization is applied to the preheat–reaction and separation sections, with the objective of minimizing the total annual cost. The dynamic response and control of the plant are evaluated for feed flow perturbations. Although the process control system acts as a first line of defense against potential hazards, other independent safety layers are discussed with safety limits specific to the critical equipment of the 2-butene metathesis unit. The results prove that the metathesis reaction of 2-butene over a mesoporous tungsten catalyst is economically attractive. For a 5.7 t/h feed rate consisting of 2-butene (70% molar) and n-butane (30% molar), a reaction–separation plant (without recycle) requires 6570 × 103 $ investment and has a profitability of 2300 × 103 $/year. Full article
(This article belongs to the Special Issue Chemical Engineering and Technology)
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13 pages, 1163 KiB  
Article
Co-Pyrolysis of Unsaturated C4 and Saturated C6+ Hydrocarbons—An Experimental Study to Evaluate Steam-Cracking Performance
by Jiří Petrů, Tomáš Herink, Jan Patera and Petr Zámostný
Materials 2023, 16(4), 1418; https://doi.org/10.3390/ma16041418 - 8 Feb 2023
Cited by 2 | Viewed by 1971
Abstract
Unsaturated C4 hydrocarbons are abundant in various petrochemical streams. They can be considered as a potential feedstock for the steam-cracking process, where they must be co-processed with C6 and higher (C6+) hydrocarbons of primary naphtha fractions. Co-pyrolysis experiments aiming at the comparison of [...] Read more.
Unsaturated C4 hydrocarbons are abundant in various petrochemical streams. They can be considered as a potential feedstock for the steam-cracking process, where they must be co-processed with C6 and higher (C6+) hydrocarbons of primary naphtha fractions. Co-pyrolysis experiments aiming at the comparison of different C4 hydrocarbon performances were carried out in a laboratory micro-pyrolysis reactor under standardized conditions: 820 °C, 400 kPa, and 0.2 s residence time in the reaction zone. C4 hydrocarbons were co-pyrolyzed with different co-pyrolysis partners containing longer hydrocarbon chain to study the influence of the co-pyrolysis partner structure on the behavior of C4 hydrocarbons. The yields of the pyrolysis products and the conversion of C4 hydrocarbons were used as the performance factors. A regression model was developed and used as a valuable tool for quantifying the inhibition or acceleration effect of co-pyrolysis on the conversion of co-pyrolyzed hydrocarbons. It was found that the performance of different C4 hydrocarbons in co-pyrolysis is substantially different from the separate pyrolysis of the individual components. Full article
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15 pages, 7417 KiB  
Article
Effect of Annealing Process and Molecular Weight on the Polymorphic Transformation from Form II to Form I of Poly(1-butene)
by Zhenkang Zhang, Yanhu Xue, Rui Li, Wei Liu, Peng Liu and Xiangling Ji
Polymers 2023, 15(4), 800; https://doi.org/10.3390/polym15040800 - 5 Feb 2023
Cited by 6 | Viewed by 2218
Abstract
Poly(1-butene) (PB-1) resin has excellent mechanical properties, outstanding creep resistance, environmental stress crack resistance and other excellent properties. However, PB-1 resin experiences a crystal transformation for a period, which seriously affects the production efficiency and directly restricts its large-scale commercial production and application. [...] Read more.
Poly(1-butene) (PB-1) resin has excellent mechanical properties, outstanding creep resistance, environmental stress crack resistance and other excellent properties. However, PB-1 resin experiences a crystal transformation for a period, which seriously affects the production efficiency and directly restricts its large-scale commercial production and application. The factors affecting the crystal transformation of PB-1 are mainly divided into external and internal factors. External factors include crystallization temperature, thermal history, nucleating agent, pressure, solvent induction, etc., and internal factors include chain length, copolymerization composition, isotacticity, its distribution, etc. In this study, to avoid the interference of molecular weight distribution on crystallization behavior, five PB-1 samples with narrow molecular weight distribution (between 1.09 and 1.44) and different molecular weights (from 23 to 710 k) were chosen to research the influence of temperature and time in the step-by-step annealing process and molecular weight on the crystal transformation by differential scanning calorimetry (DSC). When the total annealing time was the same, the step-by-step annealing process can significantly accelerate the rate of transformation from crystal form II to I. PB-1 samples with different molecular weights have the same dependence on annealing temperature, and the optimal nucleation temperature (i.e., low annealing temperature, Tl) and growth temperature (i.e., high annealing temperature, Th) were −10 °C and 40 °C, respectively. At these two temperatures, the crystal form I obtained by step-by-step annealing had the highest content; other lower or higher annealing temperatures would reduce the rate of crystal transformation. When the annealing temperature was the same, crystal form I first increased with annealing time tl, then gradually reached a plateau, but the time to reach a plateau was different. The crystalline form I contents of the samples with lower molecular weight increased linearly with annealing time th. However, the crystalline form I contents of the samples with higher molecular weight increased rapidly with annealing time th at the beginning, and then transformation speed from form II to form I slowed down, which implied that controlling Tl/tl and Th/th can tune the different contents of form I and form II. At the same Tl/tl or Th/th, with increasing molecular weight, the transformation speed from form II to form I via the step-by-step annealing process firstly increased and then slowed down due to the competition of the number of linked molecules and molecular chain mobility during crystallization. This study definitely provides an effective method for accelerating the transformation of poly(1-butene) crystal form, which not only has important academic significance, but also has vital industrial application. Full article
(This article belongs to the Section Polymer Physics and Theory)
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14 pages, 3365 KiB  
Article
Modification of the Acidic and Textural Properties of HY Zeolite by AHFS Treatment and Its Coke Formation Performance in the Catalytic Cracking Reaction of N-Butene
by Xu Lu, Chenhao Wei, Liang Zhao, Jinsen Gao and Chunming Xu
Catalysts 2022, 12(6), 640; https://doi.org/10.3390/catal12060640 - 11 Jun 2022
Cited by 7 | Viewed by 3047
Abstract
Coke formation on n-butene cracking catalyst is the main reason for the reducing of its lifetime. To study the effects of acidity and textural properties on the coke formation process, a series of HY zeolite-type catalysts were prepared by ammonium hexafluorosilicate treatment (AHFS). [...] Read more.
Coke formation on n-butene cracking catalyst is the main reason for the reducing of its lifetime. To study the effects of acidity and textural properties on the coke formation process, a series of HY zeolite-type catalysts were prepared by ammonium hexafluorosilicate treatment (AHFS). NH3-TPD and Py-IR-TPD were used to systematically study the change law of zeolite acidity. It was found that with the increase of AHFS concentration, the acid density decreased, whereas the ratio of Brønsted acid to Lewis acid first increased and then decreased. Meanwhile, the percentage of Brønsted acid inside the supper cages increased and the strength of Brønsted acid increased with the degree of dealumination. Combined with in situ IR study on coke formation, the relationship between coking and acid site was revealed. It was found that the rate of coke formation on zeolites was affected by acid density, which is the rate of coke formation decreased with the decline of acid density. When the acid density remains at the same level, it was the acid strength that determined the coke formation rate—the stronger the acid strength, the faster the coke formation rate. Full article
(This article belongs to the Topic Catalysis: Homogeneous and Heterogeneous)
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24 pages, 40023 KiB  
Review
A Review on the Production of Light Olefins Using Steam Cracking of Hydrocarbons
by Zahra Gholami, Fatemeh Gholami, Zdeněk Tišler and Mohammadtaghi Vakili
Energies 2021, 14(23), 8190; https://doi.org/10.3390/en14238190 - 6 Dec 2021
Cited by 91 | Viewed by 28502
Abstract
Light olefins are the main building blocks used in the petrochemical and chemical industries for the production of different components such as polymers, synthetic fibers, rubbers, and plastic materials. Currently, steam cracking of hydrocarbons is the main technology for the production of light [...] Read more.
Light olefins are the main building blocks used in the petrochemical and chemical industries for the production of different components such as polymers, synthetic fibers, rubbers, and plastic materials. Currently, steam cracking of hydrocarbons is the main technology for the production of light olefins. In steam cracking, the pyrolysis of feedstocks occurs in the cracking furnace, where hydrocarbon feed and steam are first mixed and preheated in the convection section and then enter the furnace radiation section to crack to the desired products. This paper summarizes olefin production via the steam cracking process; and the reaction mechanism and cracking furnace are also discussed. The effect of different operating parameters, including temperature, residence time, feedstock composition, and the steam-to-hydrocarbon ratio, are also reviewed. Full article
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14 pages, 4676 KiB  
Article
Solvent-Free Synthesis of SAPO-34 Zeolite with Tunable SiO2/Al2O3 Ratios for Efficient Catalytic Cracking of 1-Butene
by Xia Xiao, Zhongliang Xu, Peng Wang, Xinfei Liu, Xiaoqiang Fan, Lian Kong, Zean Xie and Zhen Zhao
Catalysts 2021, 11(7), 835; https://doi.org/10.3390/catal11070835 - 10 Jul 2021
Cited by 9 | Viewed by 3529
Abstract
Solvent-free synthesis methodology is a promising technique for the green and sustainable preparation of zeolites materials. In this work, a solvent-free route was developed to synthesize SAPO-34 zeolite. The characterization results indicated that the crystal size, texture properties, acidity and Si coordination environment [...] Read more.
Solvent-free synthesis methodology is a promising technique for the green and sustainable preparation of zeolites materials. In this work, a solvent-free route was developed to synthesize SAPO-34 zeolite. The characterization results indicated that the crystal size, texture properties, acidity and Si coordination environment of the resulting SAPO-34 were tuned by adjusting the SiO2/Al2O3 molar ratio in the starting mixture. Moreover, the acidity of SAPO-34 zeolite was found to depend on the Si coordination environment, which was consistent with that of SAPO-34 zeolite synthesized by the hydrothermal method. At an SiO2/Al2O3 ratio of 0.6, the SP-0.6 sample exhibited the highest conversion of 1-butene (82.8%) and a satisfactory yield of light olefins (51.6%) in the catalytic cracking of 1-butene, which was attributed to the synergistic effect of the large SBET (425 m2/g) and the abundant acid sites (1.82 mmol/g). This work provides a new opportunity for the design of efficient zeolite catalysts for industrially important reactions. Full article
(This article belongs to the Special Issue Advances in Zeolite Catalysts)
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17 pages, 1686 KiB  
Review
Zeolites as Catalysts for Fuels Refining after Indirect Liquefaction Processes
by Arno De Klerk
Molecules 2018, 23(1), 115; https://doi.org/10.3390/molecules23010115 - 6 Jan 2018
Cited by 27 | Viewed by 7057
Abstract
The use of zeolite catalysts for the refining of products from methanol synthesis and Fisher–Tropsch synthesis was reviewed. The focus was on fuels refining processes and differences in the application to indirect liquefaction products was compared to petroleum, which is often a case [...] Read more.
The use of zeolite catalysts for the refining of products from methanol synthesis and Fisher–Tropsch synthesis was reviewed. The focus was on fuels refining processes and differences in the application to indirect liquefaction products was compared to petroleum, which is often a case of managing different molecules. Processes covered were skeletal isomerisation of n-butenes, hydroisomerisation of n-butane, aliphatic alkylation, alkene oligomerisation, methanol to hydrocarbons, ethanol and heavier alcohols to hydrocarbons, carbonyls to hydrocarbons, etherification of alkenes with alcohols, light naphtha hydroisomerisation, catalytic naphtha reforming, hydroisomerisation of distillate, hydrocracking and fluid catalytic cracking. The zeolite types that are already industrially used were pointed out, as well as zeolite types that have future promise for specific conversion processes. Full article
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15 pages, 2617 KiB  
Article
An Integrated Membrane Process for Butenes Production
by Leonardo Melone, Adele Brunetti, Enrico Drioli and Giuseppe Barbieri
Processes 2016, 4(4), 42; https://doi.org/10.3390/pr4040042 - 15 Nov 2016
Cited by 4 | Viewed by 7500
Abstract
Iso-butene is an important material for the production of chemicals and polymers. It can take part in various chemical reactions, such as hydrogenation, oxidation and other additions owing to the presence of a reactive double bond. It is usually obtained as a [...] Read more.
Iso-butene is an important material for the production of chemicals and polymers. It can take part in various chemical reactions, such as hydrogenation, oxidation and other additions owing to the presence of a reactive double bond. It is usually obtained as a by-product of a petroleum refinery, by Fluidized Catalytic Cracking (FCC) of naphtha or gas-oil. However, an interesting alternative to iso-butene production is n-butane dehydroisomerization, which allows the direct conversion of n-butane via dehydrogenation and successive isomerization. In this work, a simulation analysis of an integrated membrane system is proposed for the production and recovery of butenes. The dehydroisomerization of n-butane to iso-butene takes place in a membrane reactor where the hydrogen is removed from the reaction side with a Pd/Ag alloys membrane. Afterwards, the retentate and permeate post-processing is performed in membrane separation units for butenes concentration and recovery. Four different process schemes are developed. The performance of each membrane unit is analyzed by appropriately developed performance maps, to identify the operating conditions windows and the membrane permeation properties required to maximize the recovery of the iso-butene produced. An analysis of integrated systems showed a yield of butenes higher than the other reaction products with high butenes recovery in the gas separation section, with values of molar concentration between 75% and 80%. Full article
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