Abstract: Polyoxymethylene dimethyl ethers (PODEn) as clean diesel additive can improve the combustion efficiency and quality of diesel fuel and alleviate the problem of atmospheric pollution. Considering synthetic routes, PODE production from methanol and formaldehyde is regarded as the most economical and promising synthetic route. However, methanol used for synthesizing PODE can produce water, which causes the loss of active center of catalyst and hydrolysis of PODEn in the production process. Macroporous strong acidic cation exchange resin catalyst was prepared, which has comparative advantages over other common solid acid catalysts in terms of stability and catalytic efficiency for synthesizing PODE. Catalytic reactions were carried out under 353 K, 1 MPa and 3mL·gcat-1·h-1 in a fixed bed reactor. Methanol conversion and PODE3-6 selectivity reached 49.91% and 23.43%, respectively. Catalyst lifetime evaluation showed that resin catalyst retained its catalytic activity for 20 days without significant changes and catalytic activity of completely deactivated resin catalyst can basically return to previous level by simple acid regeneration. The acid exchange capacities of original and deactivated catalyst were 2.5191 and 0.0979 mmol·g-1, respectively, while regenerated catalyst reached 2.0430 mmol·g-1, indicating that the main reason for resin catalyst deactivation is that Brønsted acid sites of original resin catalyst were temporarily replaced by non-hydrogen ion cations. A separation process consisting of extraction and distillation for PODE3-6 product was designed for separation of water and unreacted formaldehyde from reactive mixture and purification of PODE3-6, respectively. The concentration of PODE3-6 in final product can reach up to 97%. These results indicate that the scale-up production of PODE3-6 from methanol and formaldehyde solution is feasible.
Abstract: Recently, copper and manganese-containing systems are recognized as active and selective catalysts in many oxidation reactions. The main idea of this study is to obtain more information about γ-Al2O3 supported Cu-La catalysts and to evaluate their activity to simultaneous oxidation of CO, CH3OH and dimethyl ether (DME). The catalysts were synthesized by impregnation of support with a mixed aqueous solution of nitrates of copper, manganese and lanthanum under different conditions. XRD, HRTEM/EDS, TPR and thermal analysis were performed to investigate catalysts’ bulk and surface properties. The texture characteristics were determined by Quantachrome Instruments NOVA 1200e specific surface area and pore analyzer. The catalytic measurements of single compounds oxidation were carried out on continuous flow equipment with a four-channel isothermal stainless steel reactor in a wide temperature range. On the basis of XRD analysis and HRTEM/EDS, it was concluded that the active component of the mixed Cu-Mn-La/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio and consisted of at least four compounds – CuO, La2O3, MnO2 and Cu1.5Mn1.5O4. A homogeneous distribution of the active component on the carrier surface was found. The chemical composition strongly influenced catalytic properties. This influence was quite variable with regards to the different processes.
Abstract: This paper demonstrates the use of a method of synthesizing process flowsheets using a graphical tool called the GH-plot and in particular, to look at how it can be used to compare the reactions of a combined simultaneous process with regard to their thermodynamics. The technique uses fundamental thermodynamic principles to allow the mass, energy and work balances locate the attainable region for chemical processes in a reactor. This provides guidance on what design decisions would be best suited to developing new processes that are more effective and make lower demands on raw material and energy usage.
Abstract: In recent research copper and manganese systems
were found to be the most active in CO and organic compounds
oxidation among the base catalysts. The mixed copper manganese
oxide has been widely studied in oxidation reactions because of their
higher activity at low temperatures in comparison with single oxide
catalysts. The results showed that the formation of spinel
CuxMn3−xO4 in the oxidized catalyst is responsible for the activity
even at room temperature. That is why the most of the investigations
are focused on the hopcalite catalyst (CuMn2O4) as the best coppermanganese
catalyst. Now it’s known that this is true only for CO
oxidation, but not for mixture of CO and VOCs. The purpose of this
study is to investigate the alumina supported copper-manganese
catalysts with different Cu/Mn molar ratio in terms of oxidation of
CO, methanol and dimethyl ether. The catalysts were prepared by impregnation of γ-Al2O3 with
copper and manganese nitrates and the catalytic activity
measurements were carried out in two stage continuous flow
equipment with an adiabatic reactor for simultaneous oxidation of all
compounds under the conditions closest possible to the industrial. Gas
mixtures on the input and output of the reactor were analyzed with a
gas chromatograph, equipped with FID and TCD detectors. The
texture characteristics were determined by low-temperature (- 196oС)
nitrogen adsorption in a Quantachrome Instruments NOVA 1200e
(USA) specific surface area & pore analyzer. Thermal, XRD and
TPR analyses were performed. It was established that the active component of the mixed Cu-
Mn/γ–alumina catalysts strongly depends on the Cu/Mn molar ratio.
Highly active alumina supported Cu-Mn catalysts for CO, methanol
and DME oxidation were synthesized. While the hopcalite is the best
catalyst for CO oxidation, the best compromise for simultaneous
oxidation of all components is the catalyst with Cu/Mn molar ratio
1:5.
Abstract: This work studies the effect of chemical composition
on the activity and selectivity of γ–alumina supported CuO/
MnO2/Cr2O3 catalysts toward deep oxidation of CO, dimethyl ether
(DME) and methanol. The catalysts were prepared by impregnation
of the support with an aqueous solution of copper nitrate, manganese
nitrate and CrO3 under different conditions. Thermal, XRD and TPR
analysis were performed. The catalytic measurements of single
compounds oxidation were carried out on continuous flow equipment
with a four-channel isothermal stainless steel reactor. Flow-line
equipment with an adiabatic reactor for simultaneous oxidation of all
compounds under the conditions that mimic closely the industrial
ones was used. The reactant and product gases were analyzed by
means of on-line gas chromatographs.
On the basis of XRD analysis it can be concluded that the active
component of the mixed Cu-Mn-Cr/γ–alumina catalysts consists of at
least six compounds – CuO, Cr2O3, MnO2, Cu1.5Mn1.5O4,
Cu1.5Cr1.5O4 and CuCr2O4, depending on the Cu/Mn/Cr molar ratio.
Chemical composition strongly influences catalytic properties, this
influence being quite variable with regards to the different processes.
The rate of CO oxidation rapidly decrease with increasing of
chromium content in the active component while for the DME was
observed the reverse trend. It was concluded that the best
compromise are the catalysts with Cu/(Mn + Cr) molar ratio 1:5 and
Mn/Cr molar ratio from 1:3 to 1:4.
Abstract: The development of active and stable catalysts
without noble metals for low temperature oxidation of exhaust gases
remains a significant challenge. The purpose of this study is to
determine the influence of the preparation method on the catalytic
activity of the supported copper-manganese mixed oxides in terms of
VOCs oxidation. The catalysts were prepared by impregnation of γ-
Al2O3 with copper and manganese nitrates and acetates and the
possibilities for CO, CH3OH and dimethyl ether (DME) oxidation
were evaluated using continuous flow equipment with a four-channel
isothermal stainless steel reactor. Effect of the support, Cu/Mn mole
ratio, heat treatment of the precursor and active component loading
were investigated. Highly active alumina supported Cu-Mn catalysts
for CO and VOCs oxidation were synthesized. The effect of
preparation conditions on the activity behavior of the catalysts was
discussed.
The synergetic interaction between copper and manganese species
increases the activity for complete oxidation over mixed catalysts.
Type of support, calcination temperature and active component
loading along with catalyst composition are important factors,
determining catalytic activity. Cu/Mn molar ratio of 1:5, heat
treatment at 450oC and 20 % active component loading are the best
compromise for production of active catalyst for simultaneous
combustion of CO, CH3OH and DME.
Abstract: The direct synthesis process of dimethyl ether (DME)
from syngas in slurry reactors is considered to be promising because
of its advantages in caloric transfer. In this paper, the influences of
operating conditions (temperature, pressure and weight hourly space
velocity) on the conversion of CO, selectivity of DME and methanol
were studied in a stirred autoclave over Cu-Zn-Al-Zr slurry catalyst,
which is far more suitable to liquid phase dimethyl ether synthesis
process than bifunctional catalyst commercially. A Langmuir-
Hinshelwood mechanism type global kinetics model for liquid phase
DME direct synthesis based on methanol synthesis models and a
methanol dehydration model has been investigated by fitting our
experimental data. The model parameters were estimated with
MATLAB program based on general Genetic Algorithms and
Levenberg-Marquardt method, which is suitably fitting experimental
data and its reliability was verified by statistical test and residual
error analysis.
Abstract: This study presents a simulation model for converting coal to methanol, based on gasification technology with the commercial chemical process simulator, Pro/II® V8.1.1. The methanol plant consists of air separation unit (ASU), gasification unit, gas clean-up unit, and methanol synthetic unit. The clean syngas is produced with the first three operating units, and the model has been verified with the reference data from United States Environment Protection Agency. The liquid phase methanol (LPMEOHTM) process is adopted in the methanol synthetic unit. Clean syngas goes through gas handing section to reach the reaction requirement, reactor loop/catalyst to generate methanol, and methanol distillation to get desired purity over 99.9 wt%. The ratio of the total energy combined with methanol and dimethyl ether to that of feed coal is 78.5% (gross efficiency). The net efficiency is 64.2% with the internal power consumption taken into account, based on the assumption that the efficiency of electricity generation is 40%.
Abstract: It is shown that a modified UNIFAC model can be
applied to predict solubility of hydrocarbon gases and vapors in
hydrocarbon solvents. Very good agreement with experimental data
has been achieved. In this work we try to find best way for predicting
dimethyl ether solubility in liquid paraffin by using group
contribution theory.
Abstract: Dehydration of methanol to dimethyl ether (DME)
over a commercial Al2O3 catalyst was studied in an isothermal integral
fixed bed reactor. The experiments were performed on the temperature
interval 513-613 K, liquid hourly space velocity (LHSV) of 0.9-2.1h-1,
pressures between 0.1 and 1.0 MPa. The effect of different operation
conditions on the dehydration of methanol was investigated in a
laboratory scale experiment. A new intrinsic kinetics equation based
on the mechanism of Langmuir-Hinshelwood dissociation adsorption
was developed for the dehydration reaction by fitting the expressions
to the experimental data. An activation energy of 67.21 kJ/mol was
obtained for the catalyst with the best performance. Statistic test
showed that this new intrinsic kinetics equation was acceptable.
Abstract: Based on a global kinetics of direct dimethyl ether (DME) synthesis process from syngas, a steady-state one-dimensional mathematical model for the bubble column slurry reactor (BCSR) has been established. It was built on the assumption of plug flow of gas phase, sedimentation-dispersion model of catalyst grains and isothermal chamber regardless of reaction heats and rates for the design of an industrial scale bubble column slurry reactor. The simulation results indicate that higher pressure and lower temperature were favorable to the increase of CO conversion, DME selectivity, products yield and the height of slurry bed, which has a coincidence with the characteristic of DME synthesis reaction system, and that the height of slurry bed is lessen with the increasing of operation temperature in the range of 220-260℃. CO conversion, the optimal operation conditions in BCSR were proposed.
Abstract: In the present study, a heterogeneous and
homogeneous gas flow dispersion model for simulation and
optimisation of a large-scale catalytic slurry reactor for the direct
synthesis of dimethyl ether (DME) from syngas and CO2, using a
churn-turbulent regime was developed. In the heterogeneous gas flow
model the gas phase was distributed into two bubble phases: small
and large, however in the homogeneous one, the gas phase was
distributed into only one large bubble phase. The results indicated
that the heterogeneous gas flow model was in more agreement with
experimental pilot plant data than the homogeneous one.
Abstract: Homogeneous Charge Compression (HCCI) Ignition technology has been around for a long time, but has recently received renewed attention and enthusiasm. This paper deals with experimental investigations of HCCI engine using hydrous methanol as a primary fuel and Dimethyl Ether (DME) as an ignition improver. A regular diesel engine has been modified to work as HCCI engine for this investigation. The hydrous methanol is inducted and DME is injected into a single cylinder engine. Hence, hydrous methanol is used with 15% water content in HCCI engine and its performance and emission behavior is documented. The auto-ignition of Methanol is enabled by DME. The quantity of DME varies with respect to the load. In this study, the experiments are conducted independently and the effect of the hydrous methanol on the engine operating limit, heat release rate and exhaust emissions at different load conditions are investigated. The investigation also proves that the Hydrous Methanol with DME operation reduces the oxides of Nitrogen and smoke to an extreme low level which is not possible by the direct injection CI engine. Therefore, it is beneficial to use hydrous methanol-DME HCCI mode while using hydrous methanol in internal Combustion Engines.