Steam cracking of polypropylene for the production of light olefins in a fountain confined conical spouted bed reactor

Characteristics of liquid product from the pyrolysis of waste plastic mixture at low and high temperatures: Influence of lapse time of reaction

A two-step process has been used for the selective production of light olefins by the thermal cracking of high-density polyethylene. The plastic has been continuously fed into a conical spouted-bed reactor (CSBR) operating at 500 °C, which yields 93 wt % of waxes (C21+) and C12–C21 hydrocarbons. The volatile product stream has been cracked downstream in a multitubular (quartz tubes) reactor in the 800–950 °C range, with short residence times (0.016–0.032 s). A yield of 77 wt % of light olefins (C2–C4) has been obtained by operating at 900 °C in the second step. The maximum yields of ethylene, propylene, and butenes are 40.4, 19.5, and 17.5 wt %, respectively. Given the short residence time of the products in the reactor, the yield of aromatics is only 6.2 wt %. The high light olefin yield is due to the excellent performance of both steps. The CSBR allows maximizing the yield of waxes and avoiding defluidization problems. The operating conditions in the multitubular reactor (low concentration of the compou...

12 - Selective production of light olefins and hydrogen from waste plastics by pyrolysis and in-line transformation

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.

BACKGROUND: Light olefins are the basic feedstocks for the petrochemical industry. So far, the olefins yield from bio‐oil is noticeably lower than that from methanol, ethanol and naphtha, and thereby needs to be improved by optimizing catalysts and cracking conditions. The main purpose of this work is to selectively produce light olefins through the catalytic cracking of bio‐oil using the magnesium modified HZSM‐5 catalyst.RESULTSCatalytic conversion of bio‐oil and its model compounds into light olefins was performed using the Mg/HZSM‐5 catalyst. The highest olefins yield from bio‐oil was 0.25 kg olefins (kg−1 bio‐oil) with a carbon yield of 59.3 C‐mol% and nearly complete bio‐oil conversion. The reaction conditions and addition of magnesium into the HZSM‐5 zeolite can be used to control both olefins yield and selectivity. In addition, the yield of light olefins from the pyrolysis of bio‐oil is much lower than the level from bio‐oil catalytic cracking.CONCLUSIONModerately increasing the medium acid sites through addition of Mg into the zeolite effectively enhanced olefins selectivity and improved catalyst stability. The production of light olefins from bio‐oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. Copyright © 2012 Society of Chemical Industry

Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/(kg crude bio-oil). The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.

Catalytic mechanisms of methylcyclohexane cracking and light olefins production over zeolites

The production of light olefins, as the critical components in chemical industries, is possible via different technologies. The Fischer–Tropsch to olefin (FTO) process aims to convert syngas to light olefins with high selectivity over a proper catalyst, reduce methane formation, and avoid the production of excess CO2. This review describes the production of light olefins through the FTO process using both unsupported and supported iron-based catalysts. The catalytic properties and performances of both the promoted and bimetallic unsupported catalysts are reviewed. The effect of support and its physico-chemical properties on the catalyst activity are also described. The proper catalyst should have high stability to provide long-term performance without reducing the activity and selectivity towards the desired product. The good dispersion of active metals on the surface, proper porosity, optimized metal-support interaction, a high degree of reducibility, and providing a sufficient active phase for the reaction are important parameters affecting the reaction. The selection of the suitable catalyst with enhanced activity and the optimum process conditions can increase the possibility of the FTO reaction for light-olefins production. The production of light olefins via the FTO process over iron-based catalysts is a promising method, as iron is cheap, shows higher resistance to sulfur, and has a higher WGS activity which can be helpful for the feed gas with a low H2/CO ratio, and also has higher selectivity towards light olefins.

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.

Effect of the presence of light hydrocarbon mixtures on hydrogen permeance through Pd–Ag alloyed membranes

Steam thermal cracking is an established technology for the production of light olefins, such as ethylene and propylene. The shift to lighter, ethane-based feeds means that propylene production from steam crackers will be lower than the corresponding ethylene production. Therefore, alternative technologies have to be developed to produce more propylene to make up for the shortfall from steam cracking. This review looks at the steam catalytic cracking technology, which combines both catalytic cracking and steam cracking to maximize the production of light olefins. This review looks at the effect of catalyst and technology applied in fluid catalytic cracking reactors to enhance light olefins production. The influence of reaction conditions and the reaction mechanism are also presented. The graphical abstract shows the feed and steam being fed into the FCC unit from which light olefins and gasoline are produced as the desired products.

The effect of temperature, WHSV and Fe loading over HZSM-5 catalyst in thermal-catalytic cracking (TCC) of naphtha for the production of light olefins has been studied. The response surface defined by three most significant parameters is obtained from Box-Behnken design method and the optimal parameter set is found. The results show that ethylene increases with temperature, while propylene shows an optimum at 650 °C. Moderate WHSV is favorable for maximum production of light olefins. Addition of Fe to HZSM-5 has a favorable effect on the production of light olefins up to 6% of loading. Excess amount of loading decreases the conversion of naphtha, which leads to a drop in light olefin yields. The yield of light olefins (ethylene and propylene) at 670 °C, 44 hr−1 and 6 wt% Fe has been increased to 5.43 wt% compared to the unmodified HZSM-5 and reaches to 42.47 wt%.

Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM-5, MCM-41, SAPO-34 and Y-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order: HZSM-5>SAPO-34>MCM-41> Y-zeolite. The highest olefins yield from bio-oil using HZSM-5 catalyst reached 0.22 kg/kgbio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.

The treatment of wastes is one of the most important concerns of modern society, and pyrolysis is claimed as an alternative method to improve the quality of the products obtained from materials of a hydrocarbon nature such as coal and residues from petroleum distillation. The main objectives of this paper are (i) to evaluate the interactions between coal and petroleum residues (PR) which lead to a synergetic effect on the production of light olefins C1−C4 and BTX and (ii) to study the influence of variables such as temperature, pressure, and coal nature on the intensity of these effects. The study has been carried out by pyrolysis/gas chromatography in a pyroprobe using two coals (Samca and Figaredo), a petroleum residue, and mixtures of them in a mass ratio (coal/residue) of 70/30. Two temperatures, 800−900 °C, and two pressures, 0.1−1 MPa, have been studied. Different results are obtained for the individual components and the mixtures depending on the nature of the coal. In general, an increase in temperature promotes the production of both light olefins and BTX and the synergetic effects desired from the copyrolysis of the mixtures. On the other hand, increasing the pressure does not favor the production of light olefins.

Solar-driven Fischer-Tropsch synthesis represents an alternative and potentially low-cost route for the direct production of light olefins from syngas (CO and H2 ). Herein, a series of novel Co-based photothermal catalysts with different chemical compositions are successfully fabricated by H2 reduction of ZnCoAl-layered double-hydroxide nanosheets at 300-700 °C. Under UV-vis irradiation, the photothermal catalyst prepared at 450 °C demonstrates remarkable CO hydrogenation performance, affording an olefin (C2-4= ) selectivity of 36.0% and an olefin/paraffin ratio of 6.1 at a CO conversion of 15.4%. Characterization studies using X-ray absorption fine structure and high-resolution transmission electron microscopy reveal that the active catalyst comprises Co and Co3 O4 nanoparticles on a ZnO-Al2 O3 mixed metal oxide support. Density functional theory calculations further demonstrate that the oxide-decorated metallic Co nanoparticle heterostructure weakens the further hydrogenation ability of the corresponding Co, leading to the high selectivity to light olefins. This study demonstrates a novel solar-driven catalyst platform for the production of light olefins via CO hydrogenation.