丁二酰丁二酸二甲酯合成工艺研究

采用过量的丁二酸二甲酯作为反应溶剂 ,以甲醇钠与丁二酸二甲酯为原料合成丁二酰丁二酸二甲酯的合成工艺 ,研究了原料配比、反应温度及反应时间对产品收率的影响。在n(丁二酸二甲酯 )∶n(甲醇钠 ) =4 3∶1、反应温度10 0℃及回流反应时间 2 5～ 30min的最佳合成工艺条件下 ,得到质量分数为 97 5 %的丁二酰丁二酸二甲酯 ,以丁二酸二甲酯计其收率为 80 1%。     

亚磷酸二甲酯合成研究

研究了用三氯化磷和甲醇合成亚磷酸二甲酯的方法，讨论了物料配比、温度、反应时间、溶剂用量等因素对反应的影响。确定了合成亚磷酸二甲酯的最佳反应条件。在选择的试验条例上产率为８３．６％。     

对苯二甲酸二甲酯合成1,4-环己烷二甲酸二甲酯的研究进展

介绍了以对苯二甲酸二甲酯 (简称DMT)为原料 ,经催化加氢制备 1,4 环己烷二甲酸二甲酯的合成工艺 ,分析了催化剂、操作压力等对反应的影响。     

富马酸二甲酯合成研究进展

简要介绍了富马酸二甲酯的性质,包括物理性质、作用机理.重点介绍了富马酸二甲酯的合成方法,包括以富马酸、顺酐、糠醛为原料的合成方法.     

对苯二甲酸二甲酯加氢合成1,4-环己烷二甲醇

在高压反应釜中,对苯二甲酸二甲酯经两步催化加氢反应合成了1,4-环己烷:二甲醇。分别研究了反应温度、压力、反应时间和溶剂甲醇配比的影响,考察了催化剂的使用寿命。实验结果表明,Ru/Al2O3可用作对苯二甲酸二甲酯的苯环加氢催化剂,可连续使用8-10次;CuO-Cr2O3可用作1,4-环己烷二甲酸二甲酯的酯基氢解,可连续使用4-5次。此两种催化剂都具有很好的活性,在优化的反应条件下,两步加氢反应的收率都达到98%以上。     

复合催化剂一步催化合成富马酸二甲酯

实验以马来酸酐和甲醇为原料,用玻璃球负载纳米级SO42-/TiO2固体超强酸作酯化催化剂,硫脲为异构化试剂,一步催化合成富马酸二甲酯,考察了富马酸二甲酯的合成条件和催化剂的重复使用效果。最佳合成工艺条件为:n(马来酸酐)∶n(甲醇)=1∶6.0,超强酸用量2.8%,硫脲用量3.5%,回流反应3.0h,富马酸二甲酯收率为95.6%;催化剂重复使用5次富马酸二甲酯收率为89.3%。     

对苯二甲酸二甲酯的供需和生产能力

对苯二甲酸二甲酯(DMT)主要用于生产聚酯树脂、纤维和薄膜。全球DMT消费的90％以上用于生产PET聚酯,然而,新建装置为节减费用,将更经济地从PTA(对苯二甲酸)生产PET,而不是从DMT生产PET。但是,生产工程塑料宜采用DMT,生产薄膜也推荐采用DMT,因其有极好的粘附性能。     

连续化无溶剂法亚磷酸二甲酯工艺改造

针对目前亚磷酸二甲酯工业生产中存在的问题 ,通过对其合成工艺条件的研究 ,分析了该工艺的优缺点 ,提出了改进思路 ,设计了符合该合成路线的流程 ,并对连续化无溶剂法合成路线进行了改进。建立了中试装置并进行现场调试 ,集中优化了影响无溶剂法亚磷酸二甲酯收率的工艺操作参数 ,取得了满意的结果。     

合成富马酸二甲酯的固体超强酸催化剂的研究

研究了以ＺｒＯ２／ＳＯ４＝固体超强酸为催化剂催化富马酸与甲醇合成富马酸二甲酯的反应，表征了催化剂的物化性质，探讨了催化剂的制备条件、原料配比、反应时间、催化剂用量等工艺参数对收率的影响。催化剂的重复使用实验表明，ＺｒＯ２／ＳＯ４＝是富马酸二甲酯合成的较适宜的催化剂。     

马来酸二甲酯的合成研究

以顺酐和甲醇为原料,DZH型树脂为催化剂,合成了马来酸二甲酯.考察了反应温度、反应压力和进料空速对酯化反应的影响.实验结果表明,在反应温度90～110℃、反应压力0.6MPa、甲醇与顺酐质量比为1.4、顺酐空速0.74 h-1的条件下,顺酐转化率大于99.6%,二甲酯收率大于98.6%.     

Compositional modeling and simulation of dimethyl ether (DME)- enhanced waterflood to investigate oil mobility improvement

Dimethyl ether (DME) is a widely used industrial compound, and Shell developed a chemical EOR technique called DME-enhanced waterflood (DEW). DME is applied as a miscible solvent for EOR application to enhance the performance of conventional waterflood. When DME is injected into the reservoir and contacts the oil, the first-contact miscibility process occurs, which leads to oil swelling and viscosity reduction. The reduction in oil density and viscosity improves oil mobility and reduces residual oil saturation, enhancing oil production. A numerical study based on compositional simulation has been developed to describe the phase behavior in the DEW model. An accurate compositional model is imperative because DME has a unique advantage of solubility in both oil and water. For DEW, oil recovery increased by 34% and 12% compared to conventional waterflood and CO₂ flood, respectively. Compositional modeling and simulation of the DEW process indicated the unique solubility effect of DME on EOR performance.     

The performance of chemically and physically modified local kaolinite in methanol dehydration to dimethyl ether

The catalytic activity of modified natural kaolinite as a solid acid catalyst for dimethyl ether (DME) preparation was investigated by following up the conversion% of methanol and the yield% of DME. Natural kaolinite (KN) was treated chemically with H₂O₂ (KT) followed by thermal treatment at 500 °C (KC) and then mechano-chemically by ball milling with and without CaSO₄ (KB-Ca and KB, respectively). These samples were characterized by XRD, FTIR, SEM, HRTEM, TGA and NH₃-TPD techniques. The different techniques showed that the chemical treatment of kaolinite with H₂O₂ resulted in partial exfoliation/delamination of kaolinite, decreased the amount of acidic sites which is accompanied by increasing their strength. Calcination only decreased the acidic strength and slightly enlarged the particle size mostly due to heat effect. Ball milling resulted in multitude randomly-oriented crystals and increased the amount of acidic sites with the same strength of KT sample. CaSO₄ mostly produced ordered monocrystalline kaolinite and created new acidic sites with slightly lower strength relative to KB. The catalytic activity and selectivity depend on the reaction temperature, the space velocity and the strength of acid sites. The most active sample is KB-Ca, which gives 84% DME due to its high amount and strength of acidic sites. The different modification methods resulted in 100% selectivity for DME.     

二甲醚的制备与下游产品开发研究进展

本文介绍了二甲醚（ＤＭＥ）的几种生产方法,包括甲醇脱水法,合成气直接合成法和ＣＯ２加氢直接合成法,以及ＤＭＥ合成技术的最新发展情况;同时,本文还对ＤＭＥ下游产品开发研究进展进行了论述。     

The effect of physical and chemical treatment on nano-zeolite characterization and their performance in dimethyl ether preparation

Catalytic dehydration of methanol to dimethyl ether (DME) was investigated using physically and chemically modified H-Mordenite and H-Beta zeolites as catalysts. Physical modification was carried out using ultrasonic wave’s energy, while chemical modification was performed through impregnation in aluminum nitrate followed by calcination. The produced solid catalysts were evaluated as selective catalysts for the dehydration of methanol to dimethyl ether at 100–250 °C performed at three different contact times. Chemical and structural characterizations of the solid catalysts were identified using XRD, FT-IR, TEM, SEM and NH₃-TPD. Ultrasonication physical mixing of solids proved as useful tool of preparation, producing fine reordered crystals of nanocomposite zeolites with novel morphology. The newly ordered crystals were distinguished by their frame work structure, acidic properties, crystal and particle sizes, unit cell volume, pore opening, and favorable catalytic activity of 100% selectivity to DME at 200 °C for all contact times studied. The effects of Al₂O₃ on the dispersion and interaction within the nano-zeolite crystals and hence on the catalytic dehydration of methanol were verified as the major influence toward utmost selectivity.     

合成气一步法制备二甲醚双功能催化剂Cu/Al2O3的制备及性能研究

以硝酸铝和硝酸铜为氧化剂、柠檬酸为燃料,采用溶剂燃烧法制备双功能催化剂Cu/Al2O3。通过XRD,氮气吸附脱附,SEM-EDS和H2-TPR表征,结果表明该催化剂具有介孔孔道结构,并且Cu高度分散在催化剂中。在合成气一步法制备二甲醚的反应中,CO的转化率和二甲醚跌的选择性分别达到70.9%和58.8%。此外,由于高度分散的铜在高温下可以有效防止Cu的烧结聚集,反应从260°C 升温至320°C,CO转化率不断提高。     

A SINGLE-STAGE,LIQUID-PHASE DIMETHYL ETHER SYNTHESIS PROCESS FROM SYNGAS II. COMPARISON OF PER-PASS SYNGAS CONVERSION,REACTOR PRODUCTIVITY AND HYDROGENATION EXTENT

ABSTRACT

In part I of this series on the development of a single-stage, liquid-phase dimethyl ether (DME) synthesis process from syngas, the process feasibility and the process variable effects on the dual catalyst activity were discussed. This part focuses on the comparison of the single-stage reactor productivity of liquid phase methanol synthesis to that of the co-production of methanol and DME. It is experimentally demonstrated that the single-stage reactor productivity for the co-production of methanol and DME could be as much as 60% higher than that for liquid phase methanol synthesis alone. Along with this, a 50% increase in the syngas conversion is also obtained. Further, this approach is shown to co-produce methanol and DME in any fixed proportion, ranging from 5% DME to 95% DME, at significant synthesis rates of DME.     

二甲醚用作城镇燃气的技术及其经济性

国内二甲醚产能增长较快,亟待研发其安全高效利用技术,拓展利用途径,以加快推进市场化进程。城镇燃气是二甲醚利用最为现实、市场前景最为广阔的领域。开发安全、经济可行的瓶装二甲醚、LPG复合燃料供气以及以二甲醚为原料生产代天然气产品供应城市管网的技术,可以极大提高二甲醚利用量,有效破解目前国内二甲醚产能相对过剩的难题。为此,分析了二甲醚利用中存在的国家标准缺失、市场监管力度不够、产业化程度低等问题;同时对二甲醚作为替代能源的技术经济性进行了深入研究,结论指出:等热量的二甲醚价格比天然气、液化石油气分别低15%、10%以上时,就具有经济可行性。从远景看,二甲醚作为柴油汽车替代燃料市场容量大,但需要攻克的难题也较多;而作为城市管网调峰与事故应急气源,则还有许多需要用试验进行验证的技术内容。     

二甲醚在两种催化剂上裂解制低碳烯烃的反应

分别对ZSM-5分子筛催化剂和HPWO杂多酸催化剂在二甲醚催化裂解制低碳烯烃反应中的性能进行了研究。对ZSM-5分子筛催化剂,考察发现具有优良的二甲醚催化裂解活性,且在450℃时催化反应性能最优,二甲醚转化率大于90%,产物中低碳烯烃的摩尔含量也高于50%,但在该温度下催化剂易于积炭失活。对HPWO杂多酸催化剂,考察发现虽然二甲醚最优转化率较低(10%),但适宜的反应温度也较低(为300℃),且在该温度下催化剂不易发生积炭。     

二甲醚水蒸气重整催化剂的研究

采用二甲醚水解活性组分与甲醇重整活性组分机械混合的方式,制备了一系列二甲醚水蒸气重整(DMESR)双功能催化剂。分别考察了不同二甲醚水解活性组分和甲醇重整活性组分对催化性能的影响,活性测试结果表明,γ-Al2O3是最佳二甲醚水解活性组分,CuMn复合氧化物是最佳甲醇重整活性组分。两者按适当比例混合而成的CuMn/γ-Al2O3双功能催化剂具有较好的DMESR综合性能,且其最佳反应温度为350℃。在常压、350℃时,DME转化率为98.1%,H2选择性为97.5%,H2收率95.6%。     

甲醇气相催化脱水制二甲醚工艺

以甲醇为原料,氧化铝为催化剂,对甲醇气相催化脱水制气雾剂级高纯二甲醚的工艺条件进行了试验研究。结果表明,当反应温度为２８０～３３０℃,反应压力为０．８ＭＰａ时,甲醇转化率为６０％～７０％,二甲醚选择性达９９％,二甲醚质量分数为９９．９％。采用该工艺的一套２０００ｔ／ａ装置已成功运行,生产出合格的产品。