Shale hydrogenation

The hydrogenation of solid fuels is a universal method for the manufacture of liquid products; as applied to the organic matter of shale (OMS), this process can be performed at a low pressure of hydrogen because of the specific structure of OMS. Upon the hydrogenation of enriched Baltic shale at 10 MPa, a 96–98% conversion of OMS into liquid products (76–78%) and gas (18–20%) was achieved. Schematic diagrams were developed for the production of gasoline, diesel fuel, and jet engine fuel (a total yield of ∼62% on an OMS basis, fuel version), and the yield of motor fuels was 53.8% upon the separation of chemical products by liquid solvent extraction (chemical version).     

Thermal cracking of black oil fuel in a mixture with shale

The results of studies performed for the development of a new process of the thermal cracking of tar as a suspension with ground Baltic oil shale in order to obtain motor fuel components are reported. The experimental results suggest undoubted advantages of the process over industrial thermal cracking because the deep degradation of tar (the yields of a gasoline fraction with bp to 180°C, middle distillates with bp of 180–360°C, and feedstock for catalytic cracking with bp of 360–520°C were ~12, 43–44, and ~15–16 wt % on an initial tar basis) was achieved upon the single-stage processing of the raw material under relatively mild conditions (5 MPa, 425°C, and a feed space velocity of 1.0 h⁻¹). The resulting coke-like products and V and Ni contained in the raw material were deposited on the mineral matter of shale and removed from the reaction zone with the liquid products of the process.     

Manufacture of motor fuels by the hydrogenation of coals of the Itatskoe deposit

The hydrogenation of coals from the Itatskoe deposit in the Kansk-Achinsk basin was studied. It was found that low-ash power-generating coals from the Itatskoe deposit are high-quality raw materials for the production of liquid fuel, and they can be used for hydrogenation conversion into motor fuels at a hydrogen pressure of 10 MPa on an industrial scale. To obtain Euro compliant gasoline and diesel fuel components, the fractions of hydrogenated coal from the Itatskoe deposit with boiling points of <425 and 180–360°C were subjected to hydrofining in the presence of an Al-Ni-Mo catalyst from the Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences and a tungsten-nickel sulfide catalyst from the All-Russia Research Institute of Oil Refining Institute. The heat effects of typical reactions in the hydrofining process were calculated for fractions with boiling points of 55–425 and 180–360°C in the presence of the test catalysts.     

Liquefaction of municipal waste plastics in VGO over acidic and non-acidic catalysts

Co-processing of municipal waste plastics (MWP) with vacuum gas oil (VGO) over HZSM-5, DHC-8 (commercial silica-alumina catalyst) and cobalt loaded active carbon catalyst has been comparatively studied. Co-processing experiments were carried out under hydrogen atmosphere at temperatures between 425 and 450 °C. The composition, sulphur and chlorine amount of liquid products were determined. The product distribution and the composition of liquids were changed depending upon the temperature and the catalyst type. As expected temperature led to increase in cracking activity of catalysts. DHC-8 and HZSM-5 showed substantially different activities in co-processing due to the difference in their acidity. HZSM-5 gave highest gas yield at all temperatures and highest liquid yield (38.3) at low temperature. Although Co-AC was a neutral catalyst, it showed the cracking activity as well as HZSM-5 and more than DHC-8. No chlorine compound was observed in liquid products. The sulphur amount in liquid products varied with the catalyst type. Although HZSM-5 showed good cracking activity at low temperatures, it gave the liquid product containing highest sulphur amount. By considering both the quantity and quality of liquid fuel obtained from co-processing, it may be concluded that Co-AC gave the best result in the co-processing of the MWP/VGO blend. To observe the effect of metal type loaded on active carbon on catalyst activity, a series of co-processing experiments was also carried out.     

Conversion of canola oil to various hydrocarbons over Pt/HZSM-5 bifunctional catalyst

Canola oil conversion was studied at atmospheric pressure over Pt/HZSM-5 catalyst (0.5 mass% Pt) in a fixed bed micro-reactor. The operating conditions were: temperature range of 400?500°C, weight hourly space velocity (WHSV) of 1.8 and 3.6 h^?1 and steam/oil ratio of 4. The objective was to optimize the amount of gasoline range hydrocarbons in the organic liquid product (OLP) and the selectivity towards olefins and isohydrocarbons in the gas product. The gas yields varied between 22–65 mass% and were higher in the presence of steam compared to the operation without steam. The olefin/paraffin mass ratio of C₂-C₄ hydrocarbon gases varied between 0.31–0.79. The isohydrocarbons/n-hydrocarbons ratio was higher with Pt/HZSM-5 (1.6–4.8) compared with pure HZSM-5 catalyst (0.2–1.0). The OLP yields with Pt/HZSM-5 (20–55 mass% of canola oil) were slightly lower compared to HZSM-5 (40–63 mass% of canola oil) under similar conditions. The major components of OLP were aliphatic and aromatic hydrocarbons. A scheme postulating the reaction pathways for the conversion of canola oil over Pt/HZSM-5 catalyst is also presented.     

Benzene Alkylation with Propane over Mo Modified HZSM-5

Benzene alkylation with propane has been studied over HZSM-5 loading 3.1–15.4 wt% Mo in continuous-flow microreactor under 350 °C and atmospheric pressure with the highest activity obtained at 6.7 wt% Mo loading. C_7–9 aromatics were obtained as main products while the total amount of benzene rings kept unchanged. i-Propylbenzene and n-propylbenzene are formed primarily, while toluene, ethylbenzene, and ethyl-toluene are formed secondly from the propylbenzenes. Catalytic performance of 6.7 wt% Mo/HZSM-5(38) partially poisoned by NH₃ shows that the strong acid sites play a crucial role in the alkylation. Low SiO₂/Al₂O₃ ratio of HZSM-5 in the Mo modified catalysts gives high propane conversion. Two hydrothermal treatment methods were applied to the 6.7 wt% Mo/HZSM-5(38) catalyst, caused decrease of propane conversion but result in different product distribution. A possible reaction mechanism concerning bifunctional active centers resulted from combination of loaded Mo species and strong acid centers on HZSM-5 is proposed.     

Temperature effect on the viscosities of palm oil and coconut oil blended with diesel oil

One of the major difficulties in using crude vegetable oils as substitute fuels in diesel engines is their relatively high viscosities. Increasing the temperature of the crude vegetable oil, blending it with diesel oil, or the combination of both offers a simple and effective means of controlling and lowering the viscosities of vegetable oils. This work reports viscosity data, determined with a rotational bob-and-cup viscometer, for crude palm oil and cononut oil blended with diesel oil over the temperature range of 20–80°C and for different mixture compositions. All the test oil samples showed a time-independent newtonian type of flow behavior. The reduction of viscosity with increasing liquid temperature followed an exponential relationship, with the two constants of the equation being a function of the volume percentage of the vegetable oil in the mixture. A single empirical equation was developed for predicting the viscosity of these fuel mixtures under varying temperatures and blend compositions.     

Catalytic upgrading of biomass-derived oils to transportation fuels and chemicals

This paper provides a review of the catalytic upgrading of biomass-derived oils such as wood pyrolytic oils, plant/vegetable oils and tall oil to transportation fuels and useful chemicals. Both zeolite and hydrotreating type catalysts have been found suitable for upgrading which was usually done in fixed bed reactors. The hydrotreatment of pyrolytic oils at 250-450°C and 15-20 MPa H₂ pressures has been reported to yield up to 55 wt. % of liquid product containing 40-50 wt. % of gasoline range hydrocarbons. In the case of HZSM-5, the upgrading has been carried out at atmospheric pressure and 350-500°C and over 85 wt. % conversions of plant oils and tall oil have been achieved under optimum conditions. Liquid product yields from these oils were up to 70 wt. % of feed which contained 40-50 wt. % aromatic hydrocarbons. With the high pressure pyrolytic oil, pitch conversions of over 75 wt. % have been observed with HZSM-5 using co-feeds such as tetralin. However, there is only scant information available on the kinetic and mechanistic aspects of upgrading of these oils.     

Hydrocarbon conversion on ZSM-5 in the presence of N2O: relative reactivity

Conversions of methane, ethane, propane, benzene and hydrogen were studied on HZSM-5 at 418°C using binary mixtures R1:R2:N₂O:He (where R1, R2 are substances under study). Relative reactivities were determined, and it was shown that the rates of conversion of hydrocarbons are determined by the strengths of C–H bonds (H–H for hydrogen). This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic conversion of palm oil to fuels and chemicals

The conversion of palm oil to hydrocarbons using a shape selective zeolite catalyst is reported in this work. Palm oil was passed over HZSM-5 catalyst in a fixed bed micro-reactor and the reactor was operated at atmospheric pressure, a temperature range of 360 to 420°C and weight hourly space velocity (WHSV) of 2 to 4 h^?1. The main objective was to study the effect of reaction temperature and oil space velocity on the conversion and selectivity of gasoline range hydrocarbons. The results show that 40 to 70wt% of the palm oil can be converted to aromatics and hydrocarbons in the gasoline, diesel and kerosene range, light gases, coke and water. The maximum gasoline range hydrocarbons yield of 40wt% of total product formed was obtained at 400°C and 2 h^?1 space velocity.     

Operation of a gas generator controlled by supplying a gaseous oxidizer

The possibility of arranging a gas generator with the heat-release process being controlled by supplying a gaseous oxidizer is experimentally checked. Gaseous hydrogen, liquid gasoline, and solid hexamethylene tetramine (solidified alcohol) is used as a fuel. The gas generator with a proposed configuration is demonstrated to ensure stable operation during combustion of various fuels; the pressure in the gas-generator combustion chamber does not exceed the pressure of oxidizer supply and clearly correlates with variations of the oxidizer mass flow. Quasi-steady calculations allow determining all parameters of the process, including those that are not measured in the experiment. In particular, the temperature of combustion products is found to be 600–1900 K, and the gas generator forms a high-temperature mixture containing a non-reacted fuel (the air-to-fuel ratio is α = 0.55–2.30). __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 6, pp. 18–25, November–December, 2008.     

Relationship between rancimat and active oxygen method values at varying temperatures for several oils and fats

Determination of oxidative stability of different edible oils, fats, and typical fat products was made using the Rancimat method and the active oxygen method. Induction periods (IP) were recorded under controlled conditions at 110, 120, and 130 ± 0.1°C for all products and over a range of 100–160°C for selected fats. A general oil stability evaluation industrial shortenings and vanaspati to be the most stable fats, with IP ranging from 10.00 to 15.47 h. Margarine and butter samples (IP, 4.98–6.04 h) were also found to show fair oxidative stability. Among the extracted and open-market salad-grade cooking oils, rapeseed oil (IP, 4.10 h) and soybean oil (IP, 4.00 h) showed the highest oxidative stability, whereas Salicornia bigelovii oil (IP, 1.40 h) was the least stable. The induction periods of typical fat products ranged from 2.59 to 9.20 h. CV for four determinations were <5.2% for shortening and vanaspati products and <4.3% for various vegetable oils, margarine, butter, and typical fat products. Rancimat IP values obtained at 110, 120, and 130°C were 40–46, 20–25, and 9–13% of active oxygen method values, respectively, corresponding to a decrease in Rancimat IP by a factor of 1.99 with each 10°C increase in temperature. Similarly, in the temperature range 100–160°C, an increase of 10°C decreased the Rancimat IP by a factor of 1.99     

Margarine and shortening oils by interesterification of liquid and trisaturated triglycerides

Liquid vegetable oils (VO), including cottonseed, peanut, soybean, corn, and canola, were randomly interesterified with completely hydrogenated soybean or cottonseed hardstocks (vegetable oil trisaturate; VOTS) in ratios of four parts VO and one part VOTS. Analysis of the reaction products by high-performance liquid chromatography showed that at 70°C and vigorous agitation, with 0.5% sodium methoxide catalyst, the reactions were complete after 15 min. Solid-fat index (SFI) measurements made at 50, 70, 80, 92, and 104°F, along with drop melting points, indicated that the interesterified fats possess plasticity curves in the range of commercial soft tub margarine oils prepared by blending hydrogenated stocks. Shortening basestocks were prepared by randomly interesterifying palm or soybean oil with VOTS in ratios of 1:1 or 3:1 or 4:1, respectively. Blending of the interesterified basestocks with additional liquid VO yielded products having SFI curves very similar to commercial all purpose-type shortening oils made by blending hydrogenated stocks. Other studies show that fluid-type shortening oils can be prepared through blending of interesterified basestocks with liquid VO. X-ray diffraction studies showed that the desirable β′ crystal structure is achieved through interesterification and blending. Presented at AOCS Annual Meeting & Expo, Atlanta, Georgia, May 8–12, 1994.     

Preparation of bio-fuels by catalytic cracking reaction of vegetable oil sludge

Biofuel production from vegetable oil is potentially a good alternative to conventional fossil derived fuels. Moreover, liquid biofuel offers many environmental benefits since it is free from nitrogen and sulfur compounds. Biofuel can be obtained from biomass (e.g. pyrolysis, gasification) and agricultural sources such as vegetable oil, vegetable oil sludge, rubber seed oil, and soybean oil. One of the most promising sources of biofuel is vegetable oil sludge. This waste is a major byproduct of vegetable oil factories. It consists of triglycerides (61%), free fatty acid (37%) and impurities (2%). The hydrocarbon chains of triglycerides and free fatty acid are mainly made up of C₁₆ (30%) and C₁₈ (36%) hydrocarbons. The others consist of C₁₂-C₁₇ hydrocarbon chains. Transesterification can help in converting vegetable oil sludge into biofuel. The disadvantage of this method is that a large amount of methanol is required. The alternative method for this conversion is catalytic cracking. The objective of this research is to evaluate and compare the pyrolysis process with cracking catalytic reaction of vegetable oil sludge by Micro-activity test MAT 5000 of Zeton-Canada.A ZSM-5/MCM-41 multiporous composite (MC-ZSM-5/MCM-41), was successfully synthesized using silica source extracted from rice husk. The material has the MCM-41 mesoporous structure, and its wall is constructed by ZSM-5 nanozeolite crystals. The porous system of the material includes pores of the following sizes: 5 Å (ZSM-5 zeolite), 40 Å (MCM-41 mesoporous material), and another porous system whose diameter is in the range of 100-500 Å (mesoporous system) formed by the burning of organic compounds that remain in the material during the calcination process. This pore system contributes to an increase in the catalytic performance of synthesized material.The results of vegetable oil sludge cracking reaction show that the product consists of fractions such as dry gas, liquefied petroleum gas (LPG), gasoline, light cycle oil (LCO), and (heavy cycle oil) HCO, which are similar to those of petroleum cracking process.MC-ZSM-5/MCM-41 catalyst is efficient in the catalytic cracking reaction of vegetable oil sludge as it has higher conversion and selectivity for LPG and gasoline products in comparison to the pyrolysis process. Product distribution (% of oil feed) of cracking reaction over MC-ZSM-5/MCM-41 is coke (3.4), total dry gas (7.0), LPG (31.1), gasoline (42.4), LCO (8.9), HCO (7.2); and that of pyrolysis are coke (19.0), total dry gas (9.3), LPG (16.9), gasoline (28.8), LCO (13.7), and HCO (12.3).These results have indicated a new way to use agricultural waste such as rice husk for the production of promising catalysts and the processing of vegetable oil sludge to obtain biofuel.     

Catalytic conversion of canola oil to fuels and chemical feedstocks Part I. Effect of process conditions on the performance of HZSM-5 catalyst

The conversion of canola oil to hydrocarbons using a shape selective zeolite catalyst is reported in this work. Canola oil was passed over HZSM-5 catalyst in a fixed bed micro-reactor and the effects of reaction temperature and oil space velocity on the conversion and selectivity were studied using a statistical experimental design. The results show that 60–95 wt% of the canola oil can be converted to hydrocarbons in the gasoline boiling range, light gases and water. The gasoline fraction contained 60–70 wt% of aromatic hydrocarbons and the gases were mostly C₃ and C₄ paraffins. Furthermore, the spent catalyst could be regenerated completely at 600°C in 1 h with dry air.     

Catalytic cracking of endothermic fuels in coated tube reactor

Suspensoid of HZSM-5 or HY zeolites mixed with a self-made ceramic-like binder was coated on the inner wall of a tubular reactor by gas-aided fluid displacement technology. The coated zeolites were characterized by means of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The coating thickness is 10–20 μm and the particle size of the zeolites is in the range of 1–5 μm. In the coated reactor, cracking of endothermic fuels including n-dodecane and aviation fuel RP-3 was carried out separately under supercritical conditions at 600°C and 625°C to investigate their heat sinks and conversion of catalytic reactions. For the reaction catalyzed by HY (25% mass fraction) coating, the heat sink capacity of n-dodecane are 815.7 and 901.9 kJ/kg higher than that of the bare tube at 600°C and at 625°C, respectively. Conversion of n-dodecane also increases from 42% to 60% at 600°C and from 66% to 80% at 625°C. The coated zeolite can significantly inhibit the carbon deposition during supercritical cracking reactions. __________ Translated from Petrochemical Technology, 2007, 36(4): 328–333 [译自: 石油化工]     

Aqueous Extended-Surfactant Based Method for Vegetable Oil Extraction: Proof of Concept

The use of hexane to extract vegetable oil from oilseeds is of growing concern due to hexane’s environmental impact and because of worker exposure concerns. The goal of our work is to demonstrate that the aqueous extended-surfactant-based method is a viable alternative for vegetable oil extraction. In our method, ground oilseeds were dispersed in the aqueous surfactant solution, allowing the oil to be liberated from the seeds as a separate phase from the aqueous phase. The impact of pH, shaking intensity, shaking time and seed to liquid ratio on oil yield are presented. Extended-surfactants are a new type of surfactant with propoxylate (PO) and/or ethoxylate (EO) groups inserted between the hydrophilic head and the hydrophobic alkyl chain of the surfactant molecule. This unique structure of extended-surfactants enables them to produce ultralow interfacial tension with vegetable oils. We have found that at low aqueous concentrations (less than 0.3 wt%), extended-surfactant solutions are able to produce ultralow interfacial tension between aqueous extraction and vegetable oil phases. At optimum condition (seed to liquid ratio of 1–5, 30 min extraction at 150 shakes/min and 30 min centrifugation at 2,170×g) we achieved 93–95% extraction efficiency for peanut and canola oils at 25 °C. The oil quality produced from the aqueous extended-surfactant-based method was found to be comparable or even superior to that obtained from hexane-based extraction, further demonstrating the viability of aqueous extended-surfactant based extraction.     

Extraction of bitumen with sub- and supercritical water

The sub- and supercritical water extractions of Athabasca oil sand bitumens were studied using a micro reactor. The experiments were carried out in the temperature range of 360–380 °C, pressure 15–30 MPa and water density 0.07–0.65 g/cm³ for 0–2 hrs. The extraction conversion of bitumens increased with solvent power and temperature. A maximum conversion of 24% was obtained after 90 min extraction at the supercritical condition. Hydrogen and carbon mono-oxide were not detected in sub-critical region but in the supercritical region. The supercritical condition was favorable to the hydrogen formation for bitumen extraction. The extraction products were upgraded relative to the original bitumens due to direct hydrolysis of low-energy linkage and H₂ formed by water gas shift reaction in supercritical condition. 18% of initial sulfur in bitumen can be removed at maximum conversion condition. The asphaltene contents of the residue were significantly higher than that of original bitumen due to preferential extraction of aromatic compounds in supercritical condition.     

Upgrading of tall oil to fuels and chemicals over HZSM-5 catalyst using various diluents

The upgrading of crude tall oil (CTO) to fuels and chemicals was studied at atmospheric pressure and in the temperature range 370 to 440°C in a fixed bed microreactor containing HZSM-5. The oil was co-fed with diluents such as tetralin, methanol and steam. High oil conversions of the order of 80–90 wt. % were obtained using tetralin and methanol as diluents but with steam the conversion only ranged between 36 to 70 wt. %. The maximum concentration of gasoline range aromatic hydrocarbons in the liquid product was 52 and 57 wt. % with tetralin and steam but only 39 wt. % with methanol. The amount of gas product in most of the runs was 1–4 wt.%. A reaction scheme is postulated based on the results.     

锌和磷含量对Zn-P/HZSM-5催化剂芳构化性能的影响

在反应温度430 ℃、压力0.1 MPa、液时空速1 h－1条件下,进行催化裂化汽油中间馏分（75～120 ℃）的芳构化反应,考察了锌和磷含量对催化剂性能的影响。实验结果表明,当锌和磷质量分数分别为2％和4％时,改性催化剂芳构化活性及芳烃选择性最佳,其烯烃转化率、芳烃含量和芳烃收率分别为94.53 ％、68.8 ％ 和51.74 ％。