Mechanism of chain propagation for the synthesis of polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers(PODE)were synthesized from the reaction of paraformaldehyde with dimethoxymethane(DMM)over different acid catalysts at different conditions.Products were found to follow the Schulz-Flory distribution law.The chain propagation proceeds through the insertion of an individual segment of CH2O one by one,while the simultaneous insertion of a few CH2O segments or their assembly is unlikely.Due to the restriction of this law,it is difficult to increase the selectivity to the desired products(e.g.,PODE3 4).

Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.

Controllable synthesis of polyoxymethylene dimethyl ethers by ionic liquids encapsulated in mesoporous SBA-16

The promising combustion and emission properties of polyoxymethylene dimethyl ethers(PODEn)are of significant interest.However,the synthesis of PODEn products with desired chain lengths is still a problem facing synthetic PODEn.Herein,a series of unique IL@SBA16Cx solid catalysts are prepared by encapsulation of ionic liquids(ILs)within the nanocage of SBA16 through a silylation method.The structure of the encapsulated catalyst was characterized by UVvis spectra,Fourier transform infrared(FTIR),N2 adsorptiondesorption isotherms,Powder Xray diffraction(XRD),Transmission electron microscopy(TEM)and Elemental analysis.The encapsulated catalysts show similar catalytic activity to the homogeneous counterparts and display higher selectivity to the targeted PODE35 products than their homogeneous counterparts in the synthesis of PODEn from methanol(MeOH)and trioxymethylene(TOM).The encapsulated catalysts exhibit a superior PODE35 selectivity and could be the promising catalysts for PODEn synthetic reaction.

Polyoxymethylene dimethyl ethers synthesis from methanol and formaldehyde solution over one-pot synthesized spherical mesoporous sulfated zirconia

The synthesis of polyoxymethylene dimethyl ethers as an ideal diesel fuel additive is the current hot topic of modern petrochemical industry for their expedient properties in mitigating air pollutants emission during combustion.In this work,a series of spherical sulfated zirconia catalysts were prepared by a one-pot hydrothermal method assisted with surfactant cetyltrimethylammonium bromide(CTAB).The prepared sulfated zirconia catalysts were used to catalyze PODEn synthesis from methanol and formaldehyde solution.Various characterization(XRD,BET,SEM,TGA,NH_(3)-TPD,FTIR,and Py-IR)were employed to elaborate the structure–activity relationship of the studied catalytic system.The results demonstrated that S/Zr molar ratio in precursor solution played an effective role on catalyst morphology and acidic properties,where the weak Brønsted acid sites and strong Lewis acid sites were favorable to the conversion of methanol and formation of long-chain PODEn,respectively.The reaction parameters such as catalyst amount,molar ratio of FA/MeOH,reaction time,temperature and pressure were optimized.The speculated reaction pathway for PODEn synthesis was proposed based on the synergy of Brønsted and Lewis acid sites,which suggested that Brønsted and Lewis acid sites might be advantageous to the activation of polyoxymethylene hemiformals[CH_(3)(OCH_(2))_(n)OH]and methylene glycol(HOCH_(2)OH),respectively.

Investigation on combustion and emission characteristics of diesel polyoxymethylene dimethyl ethers blend fuels with exhaust gas recirculation and double injection strategy

As a kind of renewable and high oxygen content fuel,polyoxymethylene dimethyl ether(PODE)can be added in diesel to realize energy saving and emissions reduction.To evaluate the combustion and emission characteristics of a diesel engine fueled with diesel and diesel/PODE mixtures,exhaust gas recirculation(EGR)and main-pilot injection strategies with various injection timings were applied.PODE was blended with diesel by volume to form mixtures which were marked as D100(pure diesel),D90P10(90%diesel+10%PODE),and D80P20(80%diesel+20%PODE).The results showed that the ignition delay(ID)and combustion duration(CD)of D80P20 were the shortest because of the highest cetane number(CN)and high oxygen content of PODE,indicating more concentrated heat release.At low and medium loads,D80P20 achieved the highest peak heat release ratio(PHRR)and peak combustion temperature(PCT)among the three fuels,and it was 14.3%and 3.6%higher than those of D100.PODE blending with diesel can significantly reduce particulate matter(PM)and D80P20 has the lowest PM emissions at all loads.Compared with D100,both PM and nitrogen oxide(NO_(x))emissions of PODE blends decreased simultaneously with 20%EGR at all loads.With the increase of pilot-main interval,the ID and CD of all test fuels increased,while the NO_(x)and PM emissions decreased.The conclusions of the present research provide a state of the application in light-duty engines fueled with diesel/PODE blends in future work.

Optical investigation on polyoxymethylene dimethyl ethers spray flame at different oxygen levels in a constant volume vessel

In this paper,high-speed imaging and spectrometry diagnostics were used to study the spray flame structures and emission spectra of polyoxymethylene dimethyl ethers(PODE)in an optical constant volume vessel.The effects of oxygen volume fraction(15%to 80%)on some typical combustion characteristics such as spatially integrated natural intensity,flame propagation speed,lift-off length and the distribution of flame emission spectra were investigated.The results show that the PODE spray flame mainly exhibits blue chemiluminescence,which is different from the diesel yellow diffusion flame dominated by soot radiation.As the oxygen concentration increases,the flame natural luminosity and propagation speed increases,the position of lift-off region and flame tip move towards the injector nozzle,and the flame width becomes narrower.According to the spectral results,the blue chemiluminescence generated by carbon monoxide oxidation dominates the PODE flame luminescence,suggesting that no soot is formed.The increase in oxygen concentration leads to enlarged intensity and gradient of PODE flame radiation.In summary,the combination of PODE and oxygen-enriched combustion shows no soot formation and promotes the oxidation of carbon monoxide and unburned hydrocarbon.This study can provide more insights into PODE spray combustion,and offer guidelines for achieving efficient and clean combustion.

An experimental and modeling study on polyoxymethylene dimethyl ether 3(PODE_(3))oxidation in a jet stirred reactor

Polyoxymethylene dimethyl ether(PODE n,n≥1)is a class of oxygenated fuels containing unique carbon-oxygen chain structure and a promising alternative fuel for diesel engines.In this study,low-temperature oxidation characteristics of PODE_(3) were studied experimentally and numerically.Experiments were performed in a jet-stirred reactor(JSR)at equivalence ratios of 0.5,1.0 and 2.0,in the temperature range of 500 to 950 K,and at atmospheric pressure.Mole fractions of PODE_(3),O_(2),H_(2),CO,CO_(2),CH_(3) OH and C_(1)-C_(2) hydrocarbons were measured by gas chromatograph(GC).Experimental measurements were compared with the simulation results based on two literature low-temperature oxidation models,denoted as the He model and the Cai model,respectively.Good agreement was obtained between the measured and simulated fuel consumption profiles,while a deviation was observed between the experimental and simulation results on the mole fractions of O_(2) and intermediate products at medium temperatures.Reaction pathway analyses based on the two models were performed,revealing that the second O_(2)-addition reaction pathway is more significant in the prediction by the Cai model than that by the He model.Sensitivity analyses pointed out that the most important reactions affecting fuel consumption are the H-abstraction reactions of PODE_(3),and the decomposition of H_(2) O_(2) and the consumption of CH_(2)O become more sensitive at medium temperatures.