混合C_4叔丁醇法生产高纯度异丁烯工艺对比

混合C_4馏分中异丁烯和正丁烯难以通过普通蒸馏方法分离,通过将异丁烯水合生成叔丁醇,叔丁醇再脱水生成99.5%的高纯异丁烯,可实现混合C_4中异丁烯馏分的有效分离和C_4资源的高值化利用。叔丁醇水合-脱水法主要包括硫酸吸收分离工艺、离子交换树脂工艺等,分析对比不同浓度下硫酸萃取吸收分离法、Chaplits并流水合磺酸树脂法、逆流水合磺酸树脂法的发展历程、反应机理、工艺流程、工艺特点等内容,指出逆流水合离子交换树脂法工艺优于其它两种方法,并具有很好的潜在工业应用前景,其最佳操作条件反应温度80～95℃,0.25～2MPa,其异丁烯回收率90%～95%,纯度99.9%以上。     

通过Michael反应制备脂肪磺酸基强酸型阳离子交换树脂

以乙二胺化交联聚苯乙烯树脂(PS-Acyl-EDA)和2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)为原料,通过Michael反应合成脂肪磺酸基强酸型阳离子交换树脂。该磺酸基强酸型阳离子交换树脂与传统的磺酸树脂相比,具有较长的手臂链,易于和其他物质反应或进行离子交换,且避免了芳香族磺酸树脂的磺化逆反应。讨论了反应时间、反应温度、催化剂用量、试剂用量及投料比等因素对反应结果的影响。通过对反应条件的优化,可获得担载量为0~1.15mmol•g^-1的磺酸基强酸型阳离子交换树脂,并对产物进行了表征。该方法可用于色谱预装柱填料的制备。     

负载Al离子交换树脂固体催化剂的制备与应用研究

研究制备了负载Al的离子交换树脂催化剂,并对制备条件进行讨论,得到了较好的制备工艺为AlCl3与树脂的配比为8%,溶剂无水乙醇用量为80 mL,78.3℃回流反应8 h,最终铝含量为1.44 g/100 g树脂。通过红外光谱对其进行表征,结果表明732树脂在1020 cm-1处的吸收峰发生明显裂分,形成1011 cm-1和1025 cm-1两个吸收峰,说明732树脂磺酸基与AlCl3发生了络合反应,同时将其应用于丁烯二酸糠醇甲酯合成反应中取得了良好的催化效果。     

树脂催化丙烯酸水合反应动力学的研究

考察了内外扩散、反应温度和反应时间对树脂催化丙烯酸水合反应的影响,并对丙烯酸水合反应动力学进行了研究,计算了水合反应级数及反应活化能。结果表明,该水合反应级数为一级,反应活化能Ea=9.596kJ·mol-1,在此基础上初步推断了树脂催化丙烯酸水合反应机理。     

磺酸树脂催化合成7-羟基-4-甲基香豆素

研究了磺酸树脂催化合成7-羟基-4-甲基香豆素的反应，考察了反应的各种影响因素，研究表明，磺酸树脂催化合成7-羟基-4-甲基香豆素，具有较高的反应活性，可重复使用多次。该合成反应的较优工艺条件：反应温度105 ℃，n(乙酰乙酸乙酯)∶n(间苯二酚)=1∶1，磺酸树脂催化剂0.28 g,反应时间3 h，7-羟基-4-甲基香豆素收率达65.8%。     

基于共价有机骨架的固体酸催化剂合成及评价

利用多苯环单元制备的共价有机骨架材料(COFs)属于磺酸基载体,是用于固体酸催化反应的理想材料。以1,3,5-三苯氧基苯和4,4-二氯甲基联苯为结构单元,通过傅克烷基化反应制备了具有大量磺基接入位点的新型材料(COF-DT),该材料具有较大的比表面积(554 m2/g)、适当的孔体积(0. 35 cm3/g)与孔径(2. 54 nm)和良好的热稳定性与化学稳定性。COFDT表现出优异的磺酸负载能力,改性后的[HSO3]COF-DT酸中心分布均匀,单位磺酸负载量达到4. 9 mmol/g,超过传统磺酸基树脂酸量的2倍多。将[HSO3]COF-DT用于催化环己基苯氢过氧化物生产苯酚和环己酮的反应表现出优良的催化效果,原料转化率达到90. 8%,环己酮收率为94. 3%,苯酚收率为91. 1%。在循环使用多次后,依然保持良好的催化活性。     

磺酸树脂催化合成对叔丁基苯甲酸甲酯的研究

对叔丁基苯甲酸甲酯(MPTBBA)的传统催化合成方法大多具有难以分离、易腐蚀设备的问题。采用磺酸型阳离子交换树脂催化剂,系统研究了催化合成MPTBBA过程中磺酸树脂种类、反应温度、催化剂用量及原料配比对催化性能的影响。采用D001磺酸树脂为催化剂,在反应温度为120℃、甲醇与对叔丁基苯甲酸(PTBBA)摩尔比为8∶1、催化剂质量分数为10%的条件下,反应3 h PTBBA的转化率即可达到90%。对磺酸树脂催化剂的热稳定性及表面酸性的表征结果发现,催化剂具有较好的热稳定性,其催化活性与酸量有关,酸量越高磺酸树脂催化剂活性越高。该催化剂重复循环利用性能好、与产物易分离,具有广泛的工业应用前景。     

磺酸树脂催化制备低黏度二甲基硅油

以八甲基环四硅氧烷、六甲基二硅氧烷为原料,磺酸树脂为催化剂制备了低黏度二甲基硅油,并对产品进行了FT-IR表征。初步探讨了反应温度、反应时间、投料比等对二甲基硅油黏度的影响。结果表明:以质量分数2%的磺酸树脂为催化剂,八甲基环四硅氧烷与六甲基二硅氧烷的量之比14∶1,120℃反应8 h可制备出低黏度(约50 mm~2/s)二甲基硅油,且催化剂可重复利用。     

甲醇制二甲醚用全氟磺酸树脂催化剂的研究

采用溶胶-凝胶法制备了用于甲醇气相脱水制二甲醚的新型催化剂全氟磺酸树脂/二氧化硅,应用X射线衍射、红外光谱、热重-差示扫描量热、低温氮物理吸附和氨程序升温脱附法对所得催化剂进行了表征。考察了反应温度、甲醇液空速、全氟磺酸树脂含量对甲醇气相催化脱水制二甲醚反应性能和催化剂稳定性的影响。结果表明,催化剂比表面积达820m2/g,在全氟磺酸树脂负载量10.0%、甲醇液空速1h?1、反应温度184℃时,甲醇转化率92.0%,二甲醚选择性99.9%,经350h实验测试,活性和稳定性没有明显变化。     

环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成

聚甲氧基二甲醚(DMM3～7)作为柴油添加剂可提高柴油十六烷值和燃料利用率,具有广阔应用前景。以环丁砜处理后的磺酸树脂为催化剂,用于甲缩醛(DMM)和三聚甲醛(TOX)合成DMM3～7反应,系统地研究了不同条件因素对反应过程中原料转化率和产物选择性的影响,并推断了反应机理。发现:反应体系中含有不同微量(mg/kg级) H_2O对原料转化率和产物选择性影响较大;当H_2O含量超过一定值时,有白色沉淀多聚甲醛(PF)生成,PF选择性随H_2O含量增加而增大,同时生成大量甲醇,导致目标产物DMM3～7选择性降低。创新地采用环丁砜对酸性磺酸树脂NKC-9进行脱水处理,使固体催化剂表面及孔道吸附H_2O含量从2154 mg/kg显著降至198 mg/kg;同时使用13X分子筛对原料DMM进行吸附脱水处理,使DMM中H_2O含量从710 mg/kg明显降至54mg/kg。当反应温度313 K (40℃)、反应2 h、压力1.0 MPa、DMM与TOX质量比2/1时,DMM和TOX转化率以及DMM3～7质量选择性分别从48.27%、88.41%以及45.27%显著提升至52.91%、93.34%和61.58%。与文献报道的数据相比,改性后的磺酸树脂在低温下即表现出极佳的催化效果,DMM3～7质量选择性突破60%。     

草酸二丁酯的催化合成

以草酸和正丁醇为原料，分别采用不同催化剂——对甲苯磺酸和强酸性阳离子交换树脂合成草酸二丁酯，用正交实验法研究了两种催化剂对该反应的催化性能；确定了各自的最佳合成条件。以对甲苯磺酸为催化剂，在醇酸比为4：1，催化剂用量15％，回流分水1h，以苯为带水剂的反应条件下，酯收率达83．6％；以强酸性阳离子交换树脂为催化剂，在醇酸比3：1，催化剂用量10％，回流分水1．5h，以甲苯为带水剂的反应条件下，酯收率达89．5％，且催化剂可重复使用。     

Novel fluorination of polystyrene sulfonic acid resin by CF3SO3H for high stability and strong acidity

A novel fluorination method derived from CF₃SO₃H was employed to the polystyrene sulfonic acid resin, to enhance its acid strength and stability. The as-prepared CF₃SO₂-resin was characterized by FT-IR, XPS, ³¹P MAS NMR, and chemical titration, and its catalytic performance was tested. It was found that CF₃SO₂-resin exhibited higher selectivity to benzyltoluene in the Friedel–Crafts alkylation of toluene with benzyl alcohol, excellent catalytic activity with 96% conversion and a good recyclability over seven times in esterification of 1, 6-hexanedioic acid with 2-ethylhexanol.     

国内催化合成草酸二丁酯的进展

评述了对甲苯磺酸,对甲苯磺酸铜,氨基磺酸,强酸性阳离子交换树脂,六水三氯化铁,固载三氯化铝,五水四氯化锡,硫酸铜,七水硫酸锌,氧化钐,一水硫酸氢钠,硫酸氢钾,固体超强酸,杂多酸和维生素C等催化剂催化合成草酸二丁酯的合成方法。认为固载对甲苯磺酸,对甲苯磺酸铜,氨基磺酸,强酸性阳离子交换树脂,活性碳固载四氯化锡,氧化钐,一水硫酸氢钠,硫酸氢钾,固体超强酸,杂多酸和维生素C是合成草酸二丁酯的良好催化剂。微波辐射是有机合成的良好方法。     

新型脂肪族磺酸基强酸型阳离子交换树脂的合成

以2-丙烯酰胺-2-甲基丙磺酸(AMPS)为单体、CuCl/N,N,N′,N′-四甲基乙二胺(TMEDA)为催化体系,氯乙酰化聚苯乙烯微球(PS-acyl-Cl)为大分子引发剂,经原子转移自由基聚合反应(ATRP),于微球表面接枝聚脂肪族磺酸(PAMPS)链段获得脂肪族磺酸基强酸性阳离子交换树脂(PS-g-PAMPS).考察了反应温度、溶剂体系、pH 值、催化剂、反应时间等条件对接枝反应的影响,在优化的反应条件下,使用氯乙酰基担载量为3.82 mmol?g?1的 PS-acyl-Cl,10 h 可获得担载量为1.99 mmol?g?1的 PS-g-PAMPS.产物经过红外,元素分析表征.该 PS-g-PAMPS 较传统的磺酸基树脂有较长的手臂长度,位阻小,易于和其它物质反应,TG 分析显示具有很好的热稳定性.     

A MECHANISM FOR ENHANCING IONIC ACCESSIBILITY INTO SELECTIVE ION EXCHANGE RESINS

ABSTRACT

A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic / sulfonic acid resin.     

磺酸化聚苯乙烯微球催化合成N-(乙氧基亚甲基)苯胺

首先通过无皂乳液聚合制得聚苯乙烯(PS)种子乳液,再加入苯乙烯磺酸钠继续进行无皂乳液聚合,得到核壳结构的苯乙烯-苯乙烯磺酸钠共聚物微球(PS-Na SS@PS),然后酸化,得到表面磺酸化的苯乙烯-苯乙烯磺酸微球(PS-HSS@PS)。以PS-HSS@PS作为可回收的催化剂合成N-(乙氧基亚甲基)苯胺,并与对甲苯磺酸、商品化的强酸阳离子交换树脂的催化性能进行对比,结果表明,PS-HSS@PS的磺酸基含量和加入量对催化性能影响较大,磺酸基含量较高的PS-HSS@PS催化性能优异,产物收率可达97%,其活性优于强酸阳离子交换树脂(收率89%),与对甲苯磺酸相当(收率98%),且循环使用性能良好,循环使用5次,收率仍可达97%左右。     

Mesoporous silicon sulfonic acid as a highly efficient and stable catalyst for the selective hydroamination of cyclohexene with cyclohexylamine to dicyclohexylamine in the vapor phase

In this work, a new mesoporous silicon sulfonic acid catalyst derived from silicic acid has been successfully prepared by the chemical bonding method. The physicochemical properties of mesoporous silicon sulfonic acid catalysts have been systematically characterized using various techniques. The results demonstrate that sulfonic acid groups have been grafted on silicic acid by forming a new chemical bond (Si–O–S). The mesoporous silicon sulfonic acid exhibits excellent catalytic performance and stability in the vapor phase hydroamination reaction of cyclohexene with cyclohexylamine. Cyclohexene conversion of 61% and 97% selectivity to dicyclohexylamine was maintained after running the reaction for over 350 h at 280 °C. The developed mesoporous silicon sulfonic acid catalyst shows advantages of low cost, superior acid site accessibility, and long term reactivity stability. Moreover, a possible catalytic hydroamination reaction mechanism over silicon sulfonic acid was suggested. It has been demonstrated that the sulfonic acid groups of the catalyst play an important role in the hydroamination. The present work provides a simple, efficient, and environmentally friendly method for the hydroamination of cyclohexene to valuable dicyclohexylamine, which also shows important industrial application prospects.     

Partial argentation resin chromatography (PARC): I. Effect of percent silver on elution and separation of methyl octadecadienoate isomers

Partial argentation resin chromatography (PARC) for the separation of octadecadienoate ester isomers was investigated. In comparison to saturated silver resin chromatography, the time necessary to elute methylcis,cis-octadecadienaotes was dramatically shortened when columns containing sulfonic acid ion exchange resin silvered in the range of 60~90% of theoretical (meaning 60~90% of the sulfonic acid protons in the resin were replaced by silver ions) were used. Methods for preparation and silvering of the resin are discussed. The XN1010 resin (Rohm and Haas) was analyzed for total sulfonic acid groups and the amount of silver that can be incorporated by one or 2 treatments with silver nitrate was determined. A series of partially silvered resin columns was prepared and samples of methyl linoleate were eluted to study the effect of the percentage silvering on elution volumes and peak shapes. Twenty-gram samples of mixtures ofcis,trans- andtrans,trans- and oftrans,cis- andcis,cis-methyl 12,15-octadecadienoates were separated on a 91% PARC (91% silvered) column.     

Preparation and metal ion adsorption properties of the resin containing sulfonic acid groups

In this study, we explored a new ion exchange material synthesized by radical polymerization of styrene and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid by using 2,2′‐azo‐isobutyronitrile (1 mol %) and divinylbenzene (0.5 mol %) as initiator and crosslinking reagents, respectively. The resin was obtained from a large excess (90%) of styrene in the feed. The yield was 72.3%. The resin was completely insoluble in water and characterized by elemental analysis, FTIR spectroscopy, scanning electron microscopy, and thermal analysis. The metal ion retention capability was investigated for Ag(I), Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III). The effect of pH, time, and resin/metal ion mol ratio on the metal ion retention was studied. Selectivity of the resins from a mixture of metal ions and the maximum retention capacity at optimum pH were also determined. The recovery of the resin by using 1 and 4 M HClO₄ and HNO₃ demonstrated that it is possible to recover the resin above 80%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1230–1235, 2003     

羧酸和烯烃酯化反应的催化剂研究进展

综述了20世纪60年代以来羧酸和烯烃酯化合成羧酸酯反应中催化剂的研究进展,包括磺酸类催化剂、多磷酸、离子液体、硅酸盐类催化剂、沸石分子筛催化剂、离子交换树脂、杂多酸类催化剂等,比较了各类催化剂的催化活性,并展望了羧酸和烯烃酯化反应的催化剂研究方向。