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.

A Synthesis, Process Optimization, and Mechanism Investigation for the Formation of Polyoxymethylene Dimethyl Ethers

Polyoxymethylene dimethyl ethers(DMM_n) are promising diesel additives. The synthesis of DMM_n from methylal(DMM) and paraformaldehyde over the NKC-9 acidic ion-exchange resin catalyst was investigated. Many unrecyclable by-products such as methyl formate, dimethyl ether and formic acid were produced in the reaction. To increase the selectivity of the desired products DMM_(3-6) and reduce the amount of unrecyclable by-products, the effects of reaction temperature, time, pressure and the molar ratio of the raw materials were evaluated through a series of single factor experiments. Experiments revealed that trace amount of water could suppress the formation of unrecyclable by-products, and the optimum initial water content(less than 2 wt%) was investigated. In addition, the synthetic process needs to go through the polyoxymethylene hemiformals intermediate stage, and then the DMM_n were obtained when polyoxymethylene hemiformals reacted with methanol. Ultimately, a possible mechanism is proposed to describe the formation of DMM_n from polyoxymethylene hemiformals in detail, in which it is revealed that the formation of carbocation intermediates is important in the reaction processes.

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.

Formation kinetics of polyoxymethylene dimethyl ethers from methylal and trioxane with little water

Polyoxymethylene dimethyl ethers(CH_(3)-O-(CH_(2)O)_(n)-CH_(3),PODE_(n),n>1)can be added to diesel to reduce air pollution caused by incomplete combustion.Driven by this need,a cost-effective and efficient synthetic route is presented and investigated by this work for the production of PODE_(n),which are formed from methylal and trioxane with low water content(<10%(mass))over HZSM-5 catalyst in a batch slurry autoclave at the temperature from 353.15 K to 393.15 K.The reaction rate laws including the PODE_(n) and byproducts of polyoxymethylene hemiformals(HF_(n)),polyoxymethylene glycols(MG),methanol(MeOH)and methyl formate(MF)are developed.The rate constants of propagation step(k_(6))and depolymerization step(k_(-6))are assumed independent on polymerization degree of PODE_(n).The rate of reaction is proportional to the content of the catalyst(Wcat)for the catalytic reaction within the scope of the study.All kinetic parameters were estimated by combining genetic algorithm and least square regression to fit experimental data well.This work is valuable for process optimization and reactor design.

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.

聚甲氧基二甲醚-2燃烧动力学模型及试验研究

采用试验研究与动力学建模相结合方法,对聚甲氧基二甲醚-2(polyoxymethylene dimethyl ethers-2,PODE_(2))的中低温燃烧特性进行了研究。基于二甲氧基甲烷(dimethoxymethane,DMM)详细反应机理,遵循基于反应类的速率准则构建了PODE_(2)详细化学反应动力学机理,并与文献试验数据进行了验证;在快速压缩机试验平台测量了PODE_(2)在温度范围为550~900 K,当量比为0.5、1.0、2.0时着火延迟时间,结合所构建的详细反应机理,对PODE_(2)中低温条件下自着火过程控制因素进行了分析。结果表明,所构建的PODE_(2)反应机理可以很好地再现试验测量的着火延迟时间,对文献中现有的试验数据均能给出合理的预测。PODE_(2)自着火过程呈现明显的两阶段着火现象,没有表现出负温度系数(negative temperature coefficient,NTC)行为;PODE_(2)第一阶段着火延迟时间在低温段随温度呈线性变化,在720~820 K的中温范围内呈“平台”状,几乎不随温度变化。PODE_(2)低温反应活性来自于3个替代性通道,由氧加成反应开启的典型低温链分支反应序列作用被抑制。

掺混含氧燃料对混合燃料喷射特性的影响研究

为探究添加含氧燃料对燃料喷射特性的影响,将体积分数均为50%的聚甲氧基二甲醚(PODE)和正丁醇掺混于柴油制得PODE-柴油混合燃料和正丁醇-柴油混合燃料,标记为P50和B50。在高压共轨试验台上使用基于冲量法的喷射特性测试系统,研究了柴油、PODE-柴油混合燃料、正丁醇-柴油混合燃料三种燃料在多种工况下的喷射特性差异。结果表明,掺混含氧燃料对喷油速率有较大的影响:P50的体积流量小于柴油,而质量流量则相反;B50和柴油的喷油速率在低压下差异很小,但当压力升高至130 MPa时,二者的喷油速率差异明显;相同脉宽及喷射压力时与柴油相比,循环喷油量以体积计,B50大于柴油且差距随压力上升而增大,而P50则低于柴油且差距随压力上升而缩小;循环喷油量以质量计,P50和B50均高于柴油且差异率随压力上升而增大,但B50和柴油差异率的上升幅度比P50小;以喷射能量计,除小脉宽工况外,B50和P50的喷射能量均小于柴油,喷射能量由大到小排序为柴油、B50、P50。

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.

掺混策略对聚甲氧基二甲醚/甲醇双燃料燃烧影响的可视化研究

基于一台单缸光学发动机,采用高速摄影和瞬态压力同步测量方法,开展了不同掺混策略对聚甲氧基二甲醚(polyoxymethylene dimethyl ethers,PODE)/甲醇双燃料燃烧及火焰发展特性的影响研究,其中掺混策略包括P/M20(甲醇和PODE以2∶8的体积比掺混)燃料双喷射模式和缸内直喷PODE引燃预混甲醇混合气的反应活性控制压燃(reactivity-controlled compression ignition,RCCI)模式。结果表明,对于P/M20燃料双喷射模式,随着气道喷射比例增加,低温反应增强,滞燃期缩短,着火时刻显著提前,进而显著改善了燃烧稳定性;对于RCCI模式,随着气道喷射甲醇占比的增加,滞燃期延长,燃烧相位推迟,峰值压力和放热率均降低,并伴随着燃烧稳定性变差。燃烧可视化显示,两种掺混策略下,随着气道喷射比例的增加,蓝色预混火焰占比增大,最大火焰传播速度降低,由于末端未燃混合气浓度增加,火焰发展由明显的扩散燃烧逐渐转变为末端混合气不断出现新自燃点的顺序自燃模式。对比两种掺混策略可以发现,推迟缸内直喷时刻均能在一定程度上优化燃烧相位,显著改善指示热效率,然而其原因侧重点不同:对于P/M20燃料双喷射模式,提高气道喷射比例可以增强低温放热,促进着火,显著改善燃烧稳定性;对于RCCI模式,其燃烧过程主要位于上止点之后,燃烧相位更接近最佳燃烧相位,进一步减小了传热损失和循环负功,因此其具有更高的指示热效率,也更适合PODE/甲醇双燃料燃烧模式。

聚甲氧基二甲醚混合燃料喷雾特性试验研究

发展替代燃料是缓解石油能源短缺和环境污染的重要手段,在众多替代燃料中,含氧燃料因为其可再生、含碳量较低、能降低尾气排放等优势,得到了极大的发展。聚甲氧基二甲醚(PODE)、乙醇和生物柴油都是极具发展潜力的含氧替代燃料。在实际发动机中,替代燃料的喷雾行为直接影响后续的燃烧与排放过程。考虑到PODE可作为柴油-乙醇燃料的助溶剂,同时能弥补生物柴油高黏度和低挥发性的缺点,分别对柴油-乙醇-PODE和生物柴油-PODE混合燃料在定容燃烧室中的喷雾特性进行了研究。结果表明:在柴油中添加PODE对混合燃料的喷雾贯穿距(STP)影响不大,而在生物柴油中添加PODE,混合燃料的STP随着PODE比例的增加先增后减。在柴油中添加PODE和乙醇可以增加喷雾锥角(SCA),改善径向扩散,但对柴油的喷雾投影面积(SPA)影响不大,混合燃料对空气的卷吸能力与柴油相似。在生物柴油中添加PODE,混合燃料的喷雾锥角和喷雾投影面积均明显大于生物柴油,能够有效改善生物柴油的喷雾质量。

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.

基于光学发动机的柴油/聚甲氧基二甲醚引燃乙醇对比研究

为了改善内燃机燃烧与排放,探究反应活性控制压燃(reactivity controlled compression ignition,RCCI)燃烧规律,在一台轻型光学发动机上对比了缸内分别直喷柴油和聚甲氧基二甲醚(polyoxymethylene dimethyl ethers,PODE)引燃进气道喷射乙醇的燃烧特性。通过调节缸内直喷的喷油时刻和喷油比例,对燃烧过程进行了可视化试验分析。结果表明:随喷油时刻不断推迟,缸内燃烧压力与放热率呈现先增后减的趋势,喷油时刻在上止点前20°时燃烧效果最好。随着缸内直喷燃油比例的增加,每循环燃烧压力峰值和放热率峰值不断增加,燃烧相位提前,燃烧更充分。利用高速成像技术获得的图片结果显示:两种引燃模式下火焰均发生于近壁区域并向四周扩散。火焰亮度最高和面积最大的时刻出现在燃烧始点附近。PODE引燃乙醇时火焰场中无曝光区域而柴油引燃乙醇时存在较多曝光区。PODE/乙醇燃料组合相对于柴油/乙醇燃料组合的缸压和放热率峰值更高,滞燃期和燃烧持续期更短,燃烧效率更高,碳烟生成量更少。

二甲醚/聚甲氧基二甲醚-3简化机理的构建及验证

采用基于误差的直接关系图法(DRGEP)、敏感性分析法以及同分异构聚合法对二甲醚/聚甲氧基二甲醚-3(DME/DMM3)的联合详细化学反应机理进行简化,最终构建了一个包括65个组分和308个反应方程式的DME/DMM3简化化学动力学机理.为了验证其可靠性,分别用二甲醚(DME)和聚甲氧基二甲醚-3(DMM3)详细机理及试验数据与DME/DMM3简化机理计算得到的着火延迟、层流火焰燃烧速度和组分摩尔分数等进行了比较,并分析了DME/DMM3反应路径.最后验证了柴油机转速为1600r/min,当量比为0.18和0.34,燃料DME与DMM3体积配比为1∶9时的仿真与试验的缸内压力和放热率以及CO、CO_(2)、NO_(x)和HC排放物.结果表明:该DME/DMM3简化机理的着火延迟时间、层流火焰燃烧速度及射流搅拌反应器(JSR)中组分摩尔分数、缸内压力、放热率以及CO、CO_(2)、NO_(x)和HC排放物与试验值吻合良好,验证了简化机理的可靠性.

聚甲氧基二甲醚使用性能研究

从聚甲氧基二甲醚使用性能的角度,对其材料相容性、贮存安定性、与柴油的互溶性等进行了系统研究。结果表明,聚甲氧基二甲醚与常见的铜、黄铜、钢、铸铁、铸铝和焊料等金属材料的相容性总体良好,体积分数为10%的聚甲氧基二甲醚调合柴油与聚酯型聚氨酯橡胶和氟橡胶的相容性相对较好,与丁腈橡胶和聚醚型聚氨酯橡胶的相容性相对较差;在16周的43℃贮存安定性实验中,聚甲氧基二甲醚表现出良好的贮存安定性;将聚甲氧基二甲醚按照体积分数为10%的比例与车用柴油掺混后,二者具有良好的互溶稳定性。总体来说,聚甲氧基二甲醚作为柴油调合组分表现出良好的使用性能。

聚甲氧基二甲醚与柴油混合燃料的燃烧与排放特性

聚甲氧基二甲醚（PODEn）是一种高含氧、高十六烷值的新型燃料。为了降低柴油机的颗粒物排放，该文在一台轻型柴油机和一台重型柴油机上对柴油和10％、20％PODE3-4／柴油混合燃料进行了燃烧、排放和热效率的测试。结果表明：添加20％的PODE3-4，轻型柴油机大负荷工况下的碳烟排放下降90％，指示热效率能够提高2％；重型柴油机欧洲稳态循环（ESC）的颗粒物（PH）排放下降36．2％，有效热效率上升0．8％。添加PODE3-4，在指示平均有效压力（IMEP）为0．2～0．6MPa时，对放热率曲线影响不大；在IMEP为0．8MPa时，使主喷放热的滞燃期延长，主喷放热峰值增加。因此，PODE。是很有前景的柴油添加成分。

分子筛催化剂上甲醇与三聚甲醛缩合制聚甲醛二甲醚

对HY、HZSM-5、Hβ和HMCM-22分子筛催化剂上甲醇与三聚甲醛缩合制聚甲醛二甲醚(PODEn或DMMn)的反应性能进行了研究,考察了分子筛种类和酸性对产物分布的影响。结果显示,以酸性分子筛为催化剂,甲醇与三聚甲醛可缩合得到聚甲醛二甲醚。HY分子筛上反应产物主要为短链的甲缩醛(DMM);HZSM-5和Hβ分子筛上产物以DMM1～3为主,其柴油添加剂组分DMM3～8的收率分别为6.40%和13.78%;HMCM-22分子筛为催化剂时,长链的聚合物收率明显增加,其柴油添加剂组分DMM3～8的收率可以达到29.39%。NH3-TPD表征结果表明催化剂表面的酸性对产物分布有着明显的影响:表面弱酸位有利于短链产物DMM的生成,而中等强度的表面酸性位则能促进柴油添加组分DMM3～8的生成。

聚甲氧基二甲醚研究进展

聚甲氧基二甲醚(PODME)是一种有潜力的柴油添加剂,其物化性质、合成方法和催化剂被总结和评述。

聚甲氧基二甲醚及其高比例掺混柴油混合燃料发动机燃烧与排放的试验研究

为研究聚甲氧基二甲醚(PODE)及其高比例掺混柴油混合燃料对发动机燃烧与排放的影响,在一台高压油泵柱塞直径加大的云内动力2102QB柴油机上开展了柴油、PODE及30%、50%质量比掺混柴油混合燃料的燃烧与排放试验研究。发动机燃用纯PODE时排气无烟,相对于柴油,其有效热效率最高提升9.67%,并使总未燃碳氢(THC)和CO排放分别降低了50%及60%,而NOx排放增加不超过10%,因此PODE可以单独作为柴油的替代燃料。30%、50%掺混时发动机经济性略有提升,同时排气烟度及CO、THC排放均有较大幅度的改善。缸压分析燃烧过程显示,柴油中添加PODE后燃烧性能改善,滞燃期和燃烧持续期略微缩短,发动机的有效热效率提高。研究结果还表明,PODE与柴油按质量比30%掺混,可以显著降低排气烟度和有害气体排放,而不需要改变发动机的燃油供给系统。