抗高温成膜降滤失剂CMJ-1的研制及其性能

以乙烯、乙酸、甲醇和磺化剂为主要原料，通过高温氧化、酯化、聚合、醇解及磺化合成了一种新型抗高温能形成致密隔离膜的降滤失剂CMJ-1。优选出了产品的最佳磺化度，经红外光谱确认了该聚合物的基本结构，通过冷冻扫描电镜(SEM)分析，证实了CMJ-1在钻井液中能够形成致密的隔离膜，并对其成膜降滤失机理做了初步探讨。评价了它在淡水钻井液、1％和4％盐水钻井液、MMH正电胶钻井液和无机硅酸盐钻井液中的降滤失效果。实验结果表明：CMJ-1可以用作水基钻井液降滤失剂，抗温达180℃，在淡水钻井液中的最佳加量为1．O％；CMJ-1在1％和4％的盐水钻井液中也具有良好的降滤失效果，其最佳加量为2．0％；CMJ-1可用于正电胶、硅酸盐等各种水基钻井液，并与其它各种处理剂配伍性较好。     

直接甲醇燃料电池用质子交换膜研究进展

对直接甲醇燃料电池用质子交换膜的研究现状进行了概述.详细介绍了全氟磺酸型Nafion膜的结构、特性,讨论了为解决Nafion膜的 透醇问题所作的改进.综述了非氟化的质子交换膜、掺杂及共混的质子交换膜的研究进展. 简要介绍了膜的制备及测试方法.     

在镧改性HZSM-5分子筛上甲醇对噻吩转化反应的影响

探讨了在HZSM-5（硅铝摩尔比为25）分子筛催化剂上，甲醇对噻吩在固定床微型反应器中的催化脱硫转化反应规律的影响。结果表明，反应温度只有在350℃以上时，噻吩才有较大的转化率；适宜量的甲醇对噻吩的催化转化有较大的促进作用；在甲醇与溶剂苯的体积比为0．5，质量空速为14h，反应温度为350℃，剂油比为0．5时，对于1．0％La-HZSM-5分子筛催化剂，噻吩的转化率和硫化氢的产率分别达到了51．3％、18．1％，比未加甲醇时分别提高了19．8和10．0个百分点；在相同的反应条件下，对于HZSM-5分子筛催化剂，噻吩的转化率和硫化氢的产率分别达到了15．3％、6．2％，比未加甲醇时分别提高了1．1和4．0个百分点。     

甲醇在催化裂化条件下的反应研究

在甲醇作为FCC部分进料过程研究的可行性分析的基础上,对甲醇在FCC条件下的反应过程进行研究。依据FCC过程特点,采用脉冲微反一色谱装置和RGD催化剂,主要对反应温度、不同浓度甲醇水溶液、不同积炭量催化剂下的甲醇转化进行研究。得出适宜的反应条件为40％（w）甲醇水溶液进料、未积炭催化剂、反应温度5500C～600℃,烃产率可达26．3％～28．1％（w）,低碳烯烃占烃组成的67．8％～66．5％（w）。提出甲醇在FCC提升管反应器底部先于原料油进料有利于生成低碳烯烃。初步说明MTO与FCC过程结合的可行性,为进一步实验研究与应用提供依据。     

甲醇水蒸气、氧气重整制氢研究进展——质子交换膜燃料电池氢源的开发

根据质子交换膜燃料电池氢源的技术要求,本文对甲醇水蒸气、氧气重整制氢现状进行了综述,对产品气的分离与净化提出了可行的路线,为氢氧质子交换膜燃料电池最终实现装车提供了保障,为能源的有效利用和环境的有效保护提供了新思路。     

甲醇合成组分在液体石蜡中的溶解度及容积传质系数

实验测定了甲醇合成组分Ｈ２、ＣＯ、Ｎ２和ＣＯ２在液体石蜡中的平衡溶解度及容积传质系数；同时研究了甲醇、水在压力４．０～７．０ＭＰａ，温度４７３．１５～５５３．１５Ｋ下在液体石蜡中的溶解度。这些研究成果为液相法合成甲醇的研究提供了基本数据。     

一种分离碳酸二甲酯和甲醇共沸物的方法

本发明涉及一种用蒸气渗透膜分离碳酸二甲酯和甲醇共沸物的方法，将温度为64℃-120℃，压力为0．10—0．6MPa的饱和蒸汽，送人膜分离器与分离膜接触，在膜分离器的下游侧用抽真空维持真空度在4—200mmHz，碳酸二甲酯优先通过膜富集在膜的渗透侧，在真空低压下冷凝成液体，该液体混合物直接进入常压精馏塔，在塔底得到含量≥99．5％的碳酸二甲酯，在膜分离器截留侧得到高浓度甲醇，进入下一个工艺单元；分离膜是具有优先透碳酸二甲酯性能的有机复合膜、有机／无机复合膜或无机膜，本方法工艺简单、能耗小；提高了膜渗透的通量，降低了膜面积，降低投资费用；提高了安全可靠性，碳酸二甲酯纯度高。     

甲醇尿素均相催化合成氨基甲酸甲酯的研究

以甲醇和尿素为原料在有机金属催化剂均相催化下合成了氨基甲酸甲酯（MC）,优化的反应条件为：甲醇与尿素进料比为1．5（物质的量之比）,溶剂与尿素质量比为0．65,催化剂用量为0．1mol／L,反应温度160℃—170℃,反应时间为6h。在上述体系和反应条件下MC收率达83％以上,MC合成选择性为98．1％以上。     

涤纶染色改性剂SIPM合成方法的改进

采用液体三氧化硫为磺化剂对间苯二甲酸(IPA)进行磺化制得3,5-苯二甲酸-1-磺酸(磺化液),然后,在无催化剂条件下,用甲醇直接与磺化液酯化制得涤纶染色改性剂3,5-苯二甲酸二甲酯磺酸钠(SIPM).最佳磺化和酯化条件为:SO_3:IPA=1.2:1(mol),磺化温度180～190℃,磺化时间5h;MeOH:IPA=3:1(mol),酯化温度60～65℃,酯化时间1.5～3h,总收率>80%.     

羰化—氢解法低温合成甲醇的研究：II.低温液相Cu—Cr…

将自制的铜铬催化剂用于合成气制甲醇和甲酸甲酯的反应，采用搅拌釜式反应器在液相中进行，在低温低压条件下（３８３Ｋ，４．０ＭＰａ），平均反应速率达到５８．２ｇ／（Ｌ．ｈ），甲醇和甲酸甲酯的总选择性接近１００％。     

Short Side Chain Aquivion Perfluorinated Sulfonated Proton-Conductive Membranes: Transport and Mechanical Properties

Data on the water uptake, proton conductivity, diffusion permeability, cation transport selectivity, and mechanical properties of short side chain Aquivion sulfonated perfluoropolymer membranes with an equivalent weight of 870 and 965 have been described. Properties of the membranes have been compared with those of a long side chain Nafion 212 membrane (equivalent weight of 1100). An increase in the equivalent weight leads to an increase in the sorption exchange capacity and water uptake of the membranes and a decrease in their proton conductivity. The conductivity of the Aquivion membrane with an equivalent weight of 870 is 1.4–1.5 times higher than that of the Nafion 212 membrane; it reaches 13.6 mS/cm in contact with water and 1.0 mS/cm at a relative humidity of 32% at 25°C. Diffusion permeability and cation transport selectivity exhibit a nonmonotonic dependence on the equivalent weight of the material. The lowest diffusion permeability, the highest Na⁺ cation transport selectivity (99.5%), and the best mechanical properties have been found for the Aquivion membrane with an equivalent weight of 965, which is characterized by the highest degree of crystallinity.     

Feeding Methanol in an FCC Unit

The feasibility analysis of integrating methanol to olefins (MTO) with fluidized catalytic cracking (FCC) process is based on their similarities and compatibility. Feeding methanol in FCC is proposed to produce more light olefins. According to the characters of FCC, the effects of reaction temperature, water co-feed, and the coke content of catalyst in methanol conversion were studied systematically. It is concluded that high light olefins yields from methanol conversion were obtained on the FCC condition. Feeding methanol in FCC at the bottom of riser as the proper position was suggested on the ground of comparison with MGD process of FCC. The research proved the feasibility of feeding methanol in FCC and provided important reference for its commercial application in a certain degree.     

Feeding Methanol in an FCC Unit

Abstract

The feasibility analysis of integrating methanol to olefins (MTO) with fluidized catalytic cracking (FCC) process is based on their similarities and compatibility. Feeding methanol in FCC is proposed to produce more light olefins. According to the characters of FCC, the effects of reaction temperature, water co-feed, and the coke content of catalyst in methanol conversion were studied systematically. It is concluded that high light olefins yields from methanol conversion were obtained on the FCC condition. Feeding methanol in FCC at the bottom of riser as the proper position was suggested on the ground of comparison with MGD process of FCC. The research proved the feasibility of feeding methanol in FCC and provided important reference for its commercial application in a certain degree.     

甲醇自热重整制氢集成式反应器的研究

设计了一种车载集成式甲醇自热重整制氢反应器,将甲醇-水-空气自热重整制氢反应、一氧化碳变换反应、甲醇-水液体汽化、以及物料间的换热等集成于一个反应器内。自热重整区和变换区内分别装填Cr-Zn催化剂、Cu-Zn-Al变换催化剂。重整器无需外供热和附加保温措施。产物中φ(H2)可达51.1%、φ(CO)低于0.5%(干气);产氢量达到6.0 m3/h(STP);能量转化效率达到0.85。该类反应器通过甲醇的直接燃烧启动,启动时间为3m in,动态应答时间为秒级。该类型甲醇重整器可应用于车载燃料电池氢源系统。     

SBS的磺化改性

在环己烷中对苯乙烯 丁二烯 苯乙烯的三嵌段共聚物 (SBS)进行磺化改性 ,以磺化度为指标 ,通过正交实验得到的最佳工艺条件为 :反应时间 2h ,反应温度 40℃ ,浓硫酸用量 12 % (相对于SBS的质量 ) ,SBS的质量浓度 0 .2 0g mL。SBS的平均磺化度达 0 .5 4mmol g。粘接性能试验表明 ,磺化SBS胶粘剂对极性材料的粘接性能优于SBS胶粘剂     

α-Al_2O_3中空纤维复合膜的制备及其对甲醇水溶液的分离

采用聚酰胺酸(PA)-N,N-二甲基乙酰胺(DMAC)或PA-SiO2颗粒-DMAC涂膜液涂敷,通过300℃亚胺化或800℃碳化处理,对α-Al2O3中空纤维膜进行改性。在改性α-Al2O3中空纤维膜上浸涂聚乙烯醇(PVA)溶液并用戊二醛(GA)交联剂进行交联,制备α-Al2O3中空纤维渗透汽化复合膜,并对甲醇水溶液进行渗透汽化膜分离,考察了温度、料液浓度、涂膜液组成对复合膜分离性能的影响。实验结果表明,涂敷PA-DMAC涂膜液并经亚胺化的改性方式最佳,在此基础上浸涂12%(w)PVA溶液和6%(w)GA交联剂制备的复合膜分离性能较好;在温度40℃、压差100 kPa的条件下,对96%(w)甲醇水溶液的分离因子为25.0,渗透通量为15.0 g/(m2·h)。     

介孔碳基固体酸的制备及在生物柴油生产中的应用

以蔗糖为碳源、SiO_2为模板剂,采用碳化-磺化法制备介孔碳基固体酸催化剂,通过酸碱滴定、BET、XRD、FT-IR、SEM等方法对其进行表征,考察碳化温度、磺化温度对催化剂性能的影响,并将其用于大豆油与甲醇的酯交换反应,考察反应条件及原料中脂肪酸含量的影响。结果表明:制备催化剂的适宜条件为碳化温度400℃、磺化温度170℃;大豆油与甲醇酯交换反应的最佳条件为反应温度130℃、醇油摩尔比30、反应时间4h、催化剂用量(占大豆油质量的百分比)8%,生物柴油收率最高达95.94%;连续使用5次后,生物柴油收率仍达到85.46%,说明催化剂具有良好的稳定性;原料中的脂肪酸对催化剂性能有一定的负面影响,但当脂肪酸质量分数达到15%时,生物柴油收率依然可达90%以上。     

糠醛渣基水煤浆添加剂对低阶煤的成浆性能的影响与作用机制

将糠醛渣经苯酚液化和硫酸磺化改性,制备了糠醛渣基水煤浆添加剂(FRS);探讨了FRS的磺化条件对低阶煤种成浆性能的影响;系统比较了FRS与3种市售添加剂(NDF、ASDF、ZM-19)的表面官能团、磺化度、相对分子质量、Zeta电位、与煤表面的接触角等特性;分析了添加剂对水煤浆的表观黏度、流动性、稳定性方面的影响;提出了FRS与煤粒表面的作用机制。结果表明：糠醛渣的最佳磺化工艺条件为糠醛渣液化物4.0 g、浓硫酸4.0 mL、磺化温度100 ℃、磺化时间1.5 h;4种添加剂均含有亲水性的官能团(-OH和-SO3H)及疏水性的芳环,其Zeta电位绝对值与磺化度的变化趋势一致;FRS与煤表面的接触角最小,润湿性最好。在难成浆煤种的制浆质量分数58%、添加剂占煤粉质量0.2%时,FRS对水煤浆的稳定性最好,原因在于FRS使煤粒表面以水化膜彼此分开,提高了水煤浆的稳定性。     

Transport Rate of Liquid Water and Saturated Water Vapors across Polymer Proton-Exchange Membranes

Dependences of the transport rate of liquid water and saturated water vapor across commercial membranes (Nafion, MF-4SK) and proton-exchange membranes synthesized by the authors (PVDF, PP, UHMWPE, PTFE films modified with sulfonated polystyrene) on the membrane thickness have been studied. It has been found that at room temperature (17–25°C), the transport rate of liquid water and saturated water vapor across the membranes into an air stream hardly depends on the membrane type and thickness (60–240 μm), with the transport rate of saturated vapor being almost an order of magnitude below that of liquid water contacting one of the membrane surfaces. The fact that the flux of water and water vapor across the membrane does not depend on membrane thickness under conditions of maximum moistening suggests that the flow resistance is determined by the resistance at the feed and permeate interfaces. If one of the membrane surfaces is in contact with liquid water, the transport rate is equal to the rate of water removal from the permeate surface of the membrane; in the case of contact with saturated vapor, the transport rate is determined by the rate of water sorption from the vapor phase by the membrane. The results can be used to optimize the operation of fuel cells based on polymer proton-exchange membranes.