Organic Liquid Product Research Articles

Catalytic upgrading of sugarcane bagasse pyrolysis oil

Close-coupled pyrolysis and catalytic upgrading of sugarcane bagasse was carried out in a laboratory-scale apparatus under different process conditions to determine the effect of pyrolysis reactor heating rate, upgrading temperature and biomass particle size on the yield of liquid organic products. Heating rates of 40–60°C·min–1, upgrading temperatures of 385–500°C and 300–1500µm particles were used. A conventional and gallium-doped HZSM-5 catalyst was employed. Liquid product yields were in the range of 10–25%. Lower heating rates and upgrading temperatures as well as larger particle sizes gave the best liquid organic product yields. The addition of gallium to the catalyst resulted in an improved yield of benzene. The deoxygenation activity with respect to phenolic compounds remained relatively unchanged.

Conventional and microwave-assisted pyrolysis of rapeseed oil for bio-fuel production

The potential of microwave-assisted pyrolysis of rapeseed oil was evaluated in this study, based on understanding the fundamental interactions of oils with microwaves and evaluation of the product yield and composition. The pyrolysis of unused rapeseed oil (virgin oil) and simulated waste oil (SWO) was carried out using conventional and microwave-assisted heating in batch reactors. Temperatures of 500, 550 and 600°C and 300–500W microwave power were used for conventional and microwave heating respectively. Addition of 10% (w/w) HSZM-5 catalyst was also studied. The dielectric loss factor of both oil and catalyst are low, between 0.001 and 0.12, however it is possible to heat the material without the aid of microwave absorbers and this represents a key step change compared with previous studies. High conversions (70–97%) of virgin oil and SWO into gas and liquid products were achieved in conventional heating. Organic liquid products (OLP) and light bio-oil are favoured at the intermediate temperature of 550°C. Addition of catalyst did not significantly increase the conversion but increased OLP and light bio-oil yields, although there is little difference between the two oils studied. The OLP produced is within the diesel fuel range with both fractions (light and heavy bio-oils) comprising of alkanes, alkenes (between C9 and C26) and medium to long-chain fatty acids. Addition of catalyst produced an appreciable quantity of aromatic compounds and fewer acids. The condensate from microwave pyrolysis consists of aromatics, C7–C29 alkanes, cyclo-alkanes, alkenes and cyclo-alkenes; dienes, acids and other heavy oxygenated products. Interestingly, significant numbers of aromatic compounds relative to conventional treatment were detected in the microwave pyrolysis treatment. The aromatics were also found in the residual oil after microwave treatment, whereas none were found with conventional pyrolysis.

Magnesium-containing catalysts for the decarboxylation of bio-oil

At present, one of the most promising methods of processing renewable raw materials is pyrolysis, which allows liquid organic products (bio-oil) to be derived from biomass. For obtaining fuel products from bio-oil, the latter needs to be preliminarily upgraded. It is appropriate to carry out this process in two stages. The first stage—decarboxylation—is intended to reduce the corrosiveness (acidity) of the feedstock and hydrogen consumption at the second stage. Decarboxylation is usually conducted over noble metal-based catalysts. There are examples of employing cheaper catalysts based on alkaline-earth metals; however, these catalysts suffer from insufficient stability. Here, we report the activity of MgO-based catalysts in the decarboxylation of pentanoic acid, a model compound imitating bio-oil, and the effect of dopants on the stability of the magnesium-containing catalysts. The process has been carried out in an inert atmosphere at a temperature of 350°C and a pressure of 0.50 MPa. Raising the MgO calcination temperature to 1200°C and introducing stabilizing admixtures (Al2O3, SiO2, and ZrO2) affords catalysts that are mainly deactivated via carbonate formation rather than the formation of soluble magnesium salts and are, therefore, more promising from the standpoint of regenerability.

Support effects on hydrotreating of soybean oil over NiMo carbide catalyst

As an alternative to conventional sulfide catalysts, NiMo carbide catalysts were prepared by impregnation method and studied for the hydrotreating of soybean oil to produce hydrocarbons in the gasoline to diesel range. The effect of the catalyst supports on activity and selectivity was investigated by using three different types of materials: mesoporous material (Al-SBA-15), alumina (γ-Al2O3) and zeolites (ZSM-5, Zeolite β and USY). The structural characterization of the catalysts was performed using XRD, BET and TEM. Catalytic tests were carried out in a bench scale flow reactor at 400°C and 650psi. The results showed that the Al-SBA-15 supported catalyst has the highest surface area of 711.5m2g−1 and largest pore volume of 0.71cm3g−1. Among the five catalysts, hydrotreating on NiMoC/Al-SBA-15 gave the highest yield of organic liquid product (96%) and highest selectivity (97%) to hydrocarbons in the boiling range of the diesel fraction. For the three zeolite-supported catalysts, hydrotreating of soybean oil produced more hydrocarbon products in the boiling range of green gasoline (about 15–40%).

Preparation and formation mechanism of levoglucosan from starch using a tubular furnace pyrolysis reactor

Tubular furnace pyrolysis reactor for the production of organic liquids from biomass has been demonstrated at a pilot-scale of 500g/batch of dry feed at a temperature of 360–420°C. Treatment of starch gives high yields of 1,6-anhydro-β-d-glucopyranose (levoglucosan, LG). The yield depends on the heater temperature and the vacuum pressure in the reactor. The maximum yield of levoglucosan from corn starch is about 56% (analytical value) at ultimate pressure of 6×10−2Pa, pumping speed of 15L/s and temperature of 390°C. Under the same conditions, the products of levoglucosan pyrolysis are exactly the same as starch pyrolysis. Based on these experimental results and further thermal analysis, a new pyrolysis mechanism is provided and discussed.

THE EFFECT OF TEMPERATURE PYROLYSIS PROCESS OF USED TIRES ON THE QUALITY OF OUTPUT PRODUCTS

Abstract Pyrolysis together with gasification and combustion create a group of so called thermic processes. Unlike the combustion it is based on thermic decomposition of organic materials without any access of oxidative media. Within the pyrolytic process, three main fractions are created: solid residue, pyrolytic gas and organic liquid product - pyrolytic oil. The presented article examines the effects of pyrolysis operational conditions (above all, temperature) on gas products, solid residues and liquid fractions.

Extraction of Fatty Acids from Noncatalytically Cracked Triacylglycerides with Water and Aqueous Sodium Hydroxide

A study was performed to determine the effectiveness of extracting short-chain fatty acids (SCFAs) from noncatalytically cracked canola oil using neutral and basic aqueous solutions. A detailed quantitative analysis was performed to determine the composition of the cracking reactor organic liquid product (OLP) before and after extraction. We have demonstrated that water alone can be used to completely extract C2 and C3 monocarboxylic acids, while partially extracting acids up to C6. The degree of extraction can be slightly increased by increasing temperature and, for some acids, by using multiple extraction stages. A basic solution (1 M NaOH) was found to extract a wider range of acids—up to C8—and this was independent of the temperature or number of stages. While this method was not capable of reducing the acid number of the OLP to within the specifications for fuel, it could be used to extract a narrow range (C2 to C5) of biobased carboxylic acids. As such, this method could serve as one step in a process to produce biobased carboxylic acids, replacing acids currently produced from non-renewable sources.

Method development for the characterization of biofuel intermediate products using gas chromatography with simultaneous mass spectrometric and flame ionization detections

Accurate analytical methods are required to develop and evaluate the quality of new renewable transportation fuels and intermediate organic liquid products (OLPs). Unfortunately, existing methods developed for the detailed characterization of petroleum products, are not accurate for many of the OLPs generated from non-petroleum feedstocks. In this study, a method was developed and applied to the detailed characterization of complex OLPs formed during triacylglyceride (TG) pyrolysis which is the basis for generating one class of emerging biofuels. This method uses gas chromatography coupled simultaneously with flame ionization and mass spectrometry detectors (GC–FID/MS). The FID provided accurate quantification of carbonaceous species while MS enabled identification of unknown compounds. A programed temperature vaporizer using a 25 °C, 0.1 min, 720 °C min −1, 350 °C, 5 min temperature program is employed which minimizes compound discrimination better than the more commonly utilized split/splitless injector, as verified with injections at 250 and 350 °C. Two standard mixtures featuring over 150 components are used for accurate identification and a designed calibration standard accounts for compound discrimination at the injector and differing FID responses of various classes of compounds. This new method was used to identify and quantify over 250 species in OLPs generated from canola oil, soybean oil, and canola methyl ester (CME). In addition to hydrocarbons, the method was used to quantify polar (upon derivatization) and unidentified species, plus the unresolved complex mixture that has not typically been determined in previous studies. Repeatability of the analytical method was below 5% RSD for all individual components. Using this method, the mass balance was closed for samples derived from canola and soybean oil but only ca. 77 wt% of the OLP generated from CME could be characterized. The ability to close the mass balance depended on sample origin, demonstrating the need for an accurate quantification method for biofuels at various stages of production.

Radiation and postradiation distillation of biopolymers: Lignin and chitin

Lignin and chitin were decomposed in the regimes of postradiation dry distillation and distillation under conditions of radiation heating by accelerated electrons. The distilled off condensates consisted of two phases: brown viscous tar and lighter aqueous organic solution. The preliminary irradiation of lignin did not change the yield of distilled off tar, but it increased the fraction of alkoxyphenols in this tar. In the postradiation distillation of chitin, the yield of tar decreased with the dose. The effective distillation of biopolymers under radiation heating conditions was observed at dose rates higher than ∼1 kGy/s. The condensate distilled off at a dose rate of 1.5–2.5 kGy/s differed from the product of standard dry distillation in a higher yield of liquid organic products.

Extraction of Fatty Acids from Noncatalytically Cracked Triacylglycerides Using Aqueous Amines

It has been reported that a basic aqueous solution was effective in extracting short chain C2–C6 fatty acids from noncatalytically cracked triacylglyceride oils. However, the extraction efficiency was not optimal over the entire range (C2–C12) of acids present in the cracking reactor organic liquid product (OLP). Therefore, an additional study was performed to explore the efficiency of solvent extraction using aqueous amines for this application. Based on the screening of several amines, two tertiary amines, trimethyl amine (TMA), and dimethyl ethanolamine (DMEA), were selected and evaluated. The extraction conditions were optimized with respect to several factors: temperature, amine concentration, and the amine-to-OLPratio (amine/OLP). Under optimal conditions, both TMA and DMEA were effective in extracting a wide range of organic acids, with TMA removing 93% of total acids and DMEA removing 100% of total acids. The amine/OLP was found to be a significant factor, as was the concentration of the amine solution. Temperature was not found to be a significant factor over the range studied. These results provide a basis for the development of a scalable, continuous process to produce a variety of C2–C12 fatty acids from biological sources.

Production of biofuel from waste cooking palm oil using nanocrystalline zeolite as catalyst: Process optimization studies

The catalytic cracking of waste cooking palm oil to biofuel was studied over different types of nano-crystalline zeolite catalysts in a fixed bed reactor. The effect of reaction temperature (400–500°C), catalyst-to-oil ratio (6–14) and catalyst pore size of different nanocrystalline zeolites (0.54–0.80nm) were studied over the conversion of waste cooking palm oil, yields of Organic Liquid Product (OLP) and gasoline fraction in the OLP following central composite design (CCD). The response surface methodology was used to determine the optimum value of the operating variables for maximum conversion as well as maximum yield of OLP and gasoline fraction, respectively. The optimum reaction temperature of 458°C with oil/catalyst ratio=6 over the nanocrystalline zeolite Y with pore size of 0.67nm gave 86.4wt% oil conversion, 46.5wt% OLP yield and 33.5wt% gasoline fraction yield, respectively. The experimental results were in agreement with the simulated values within an experimental error of less than 5%.

In-situ upgrading of biomass pyrolysis vapors: Catalyst screening on a fixed bed reactor

In-situ catalytic upgrading of biomass fast pyrolysis vapors was performed in a fixed bed bench-scale reactor at 500°C, for catalyst screening purposes. The catalytic materials tested include a commercial equilibrium FCC catalyst (E-cat), various commercial ZSM-5 formulations, magnesium oxide and alumina materials with varying specific surface areas, nickel monoxide, zirconia/titania, tetragonal zirconia, titania and silica alumina. The bio-oil was characterized measuring its water content, the carbon–hydrogen–oxygen (by difference) content and the chemical composition of its organic fraction. Each catalytic material displayed different catalytic effects. High surface area alumina catalysts displayed the highest selectivity towards hydrocarbons, yielding however low organic liquid products. Zirconia/titania exhibited good selectivity towards desired compounds, yielding higher organic liquid product than the alumina catalysts. The ZSM-5 formulation with the highest surface area displayed the most balanced performance having a moderate selectivity towards hydrocarbons, reducing undesirable compounds and producing organic liquid products at acceptable yields.

New path in the thermal cracking of triacylglycerols (canola and soybean oil)

Triacylglycerols (TGs) are naturally occurring oils abundant in many crops. A series of batch uncatalyzed thermal decomposition experiments were performed using canola and soybean oils to explore pathways of TG cracking. A detailed gas chromatographic protocol based on mass spectrometric identification and flame ionization quantification was applied to the organic liquid product generated upon cracking. Reaction conditions were identified that resulted in a novel organic liquid product (OLP) composition compared to previously reported work. Under these conditions (temperatures within a 420–440°C range) a new route for TG thermolysis was discovered in which cracking reactions of original TG-bound fatty acids were nearly complete and led to the formation of 15–25wt.% C2–C10 linear saturated monocarboxylic acids and ca. 30% linear alkanes. Less than 2wt.% C16–C18 fatty acids which were originally present in the feedstocks as glycerol triesters were found in the OLP. These reactions appear to be kinetically controlled due to abundant hydrogen formation. This route provides a significant enrichment of low-MW compounds in the OLP (65–70wt.% being <C11) and thus may be considered as a new option for the production of replacement products for petroleum-based fuels and chemicals.

Catalytic cracking of squalene to gasoline-range molecules

Cracking squalene over a zeolite catalyst produced an organic liquid containing light hydrocarbons. The distillate of the organic liquid product (b.p. <275 °C) was analyzed by ASTM gasoline methods and found to have a research octane number of 98.

Catalytic cracking of bio-oil to organic liquid product (OLP)

The main objective of this paper is to find the optimum operating condition to upgrade the EFB-derived pyrolysis oil (bio-oil) to liquid fuel, mainly gasoline using Taguchi Method. From the analysis that has been done, it is found that the optimum operating condition for heterogeneous catalytic cracking process is at 400 °C, 15 min of reaction time using 30 g of catalyst weight where operating at this condition produced the highest yield of gasoline fraction which is 91.67 wt.%. This observation proves that EFB-derived pyrolysis oil could be upgraded via heterogeneous catalytic cracking to produce gasoline.

Comparison of canola oil conversion over MFI, BEA, and FAU

The catalytic conversion of canola oil was performed at atmospheric pressure with a weight hourly space velocity of 1.0 h −1 in a fixed-bed reactor at temperatures of 400 °C and 450 °C over MFI, BEA, and FAU, and with different SiO 2/Al 2O 3 ratios for BEA and FAU. Simulated distillation of the organic liquid product showed that MFI gave the highest gasoline range product (39%, 450 °C) and lowest coke (3.2%, 450 °C) yields compared to the other zeolites. MFI produced the most C 3 hydrocarbons, while BEA produced the most C 4s and FAU generated the most C 5s. As SiO 2/Al 2O 3 in BEA increased from 25 to 300, the gasoline fraction yield increased from 18.5% to 25.0% at 400 °C.

Electron beam conversion of cellulose into liquid organic products

Cotton and pine cellulose was distilled under the heating with a beam of accelerated electrons (∼2 kGy/s) in a flow of gaseous alkanes. An organic liquid (∼60 wt %), gas (13–18 wt %), and charcoal were the products. Carbonyl compounds and furans dominate in the composition of the liquid. It is supposed that electron beam processing has a combined effect including preliminary radiolytic modification of cellulose, the initiation of its radical-chain destruction, and strong rapid warming-up within tracks.

Thermogravimetric study of the thermal degradation of solid and liquid organic carbon-containing products

The thermolysis of D-grade (long-flame) coal, refinery waste, coal-processing waste, and biomass was studied by thermogravimetry in order to increase the total efficiency of the thermal processing of organic carbon-containing products and the selectivity of formation of particular by-products (solid, gaseous, or liquid). The deconvolution of the resulting thermogravimetric curves was performed using SCIENTIST 3.0 software. In accordance with published concepts, it was proposed to separate the thermal degradation of complex multicomponent solid or liquid starting products into individual components and to relate them to the thermolysis of particular structural fragments of the starting carbon-containing materials. Quantitative (yield/temperature) and qualitative (composition/nature) data were obtained for the conversion of individual structural fragments in complex multicomponent organic materials. In addition, the effect of alkali metal carbonate additives on the thermolysis of the individual structural fragments of the test products was analyzed.

Electron-beam degradation of wood: 1. Dry distillation products

Electron-beam heating to ≥270°C initiates the process of dry (destructive) distillation of wood. Birch, aspen, alder, spruce, and pine wood is decomposed yielding liquid organic products (55–61 wt %), gas (13–18 wt %), and charcoal. The liquid largely consists of carbonyl compounds. The furan fraction makes up approximately one fifth. The liquid produced from softwood is heavier and is rich in phenolic compounds. The products of dry distillation upon wood irradiation in a stream of propane and butanes are enriched in liquid alkanes, alcohols, and ethers. The feasibility of conversion of the condensable products into regular liquid fuel is discussed.

Effect of catalyst additives on the production of biofuels from palm oil cracking in a transport riser reactor

Catalytic cracking of crude palm oil (CPO) and used palm oil (UPO) were studied in a transport riser reactor for the production of biofuels at a reaction temperature of 450 °C, with residence time of 20 s and catalyst-to-oil ratio (CTO) of 5 g g −1. The effect of HZSM-5 (differrent Si/Al ratios), beta zeolite, SBA-15 and AlSBA-15 were studied as physically mixed additives with cracking catalyst Rare earth-Y (REY). REY catalyst alone gave 75.8 wt% conversion with 34.5 wt% of gasoline fraction yield using CPO, whereas with UPO, the conversion was 70.9 wt% with gasoline fraction yield of 33.0 wt%. HZSM-5, beta zeolite, SBA-15 and AlSBA-15 as additives with REY increased the conversion and the yield of organic liquid product. The transport riser reactor can be used for the continuous production of biofuels from cracking of CPO and UPO over REY catalyst.