β-分子筛催化剂在异丙苯生产中的应用研究

以大连理工大学BPA分子筛催化苯-丙烯烷基化合成异丙苯小试成果为基础,利用中国石油吉林石化研究院中试装置合成改性β-分子筛催化剂,并在中国石油吉林石化双苯厂大生产装置进行了侧线挂管实验,通过翔实的实验数据论证了研制的β-分子筛催化剂取代进口美国UOP公司QZ-2000分子筛催化剂的可能性。同时,通过工艺条件实验探讨了研制β-分子筛催化剂的最优工艺参数。研制分子筛催化剂在催化苯-丙烯烷基化反应中,苯转化为异丙苯的选择性为92.17%,转化为二异丙苯的选择性为7.69%,总异丙基化选择性为99.86%。自制的2.5 t分子筛催化剂已于2005年用于工业生产的一个床层,效果良好。     

UOP公司生产异丙苯新工艺

美国环球油品公司用高选择性和高稳定性沸石催化剂QZ- 2 0 0 0生产异丙苯的 Q- Max工艺所得异丙苯纯度的质量分数大于 99.97% ,质量收率大于 99.97%。所用的 QZ- 2 0 0 0催化剂完全可再生 ,避免了以前采用磷酸催化剂和三氧化铝催化剂时的催化剂处理问题。与其他用沸石催化剂生产异丙苯的技术相比 ,Q- Max工艺所得异丙苯的杂质含量低 ,热联合好 ,因而生产成本低 ,而且只用一个反应器。第 1套 Q- Max工业装置于 1996年 8月在 JL M化学品公司投产 ,该装置由原来的磷酸催化剂装置改造而成。该装置用最初装填的催化剂一直运转 ,已达到异丙…     

YSBH-3分子筛催化剂上苯与丙烯泡点烷基化工艺条件

采用等温固定床积分反应器,对YSBH-3分子筛催化剂上苯与丙烯烷基化合成异丙苯进行了实验研究,系统考察了反应体系相态变化(液相反应泡点反应气相反应)对YSBH-3分子筛催化剂性能的影响,并与工业YSBH-3分子筛催化剂的液相烷基化(操作压力3 MPa)结果进行了对比分析。结果表明(1)YSBH-3分子筛催化剂在2 MPa操作压力下的性能明显优于3 MPa操作压力下的性能,具有更高的异丙苯选择性和更低的二异丙苯和三异丙苯选择性;(2)与2 MPa下气相和液相烷基化结果相比,2 MPa泡点温度下进行苯与丙烯烷基化具有最高的异丙苯选择性,更低的二异丙苯、三异丙苯和正丙苯选择性。这一结论对提高工业装置的异丙苯产品质量、降低后续分离工段负荷和减少烷基转移反应器处理量非常有利。以单因素实验法系统考察了液相空速(5~35 h-1)和苯与丙烯的物质的量之比(5~12)对2 MPa压力下、苯与丙烯泡点烷基化的影响,最终确定的相对适宜泡点烷基化工艺条件范围为:压力2 MPa,苯与丙烯的物质的量之比8:1~10:1(对应的泡点温度为176~184℃),液相空速8~11 h-1。在此条件下,丙烯转化率保持在99%以上,异丙苯和二异丙苯选择性分别保持在86%和13%左右。     

苯与重芳烃烷基转移反应工艺研究

在FTH-2催化剂上,考察反应原料物质的量比、反应温度和液体原料空速对苯与二异丙苯及以三异丙苯为主的重芳烃烷基转移反应的影响。结果表明,苯与二异丙苯烷基转移反应较适宜的条件为:n(苯)∶n(二异丙苯)=10,反应温度215℃,反应压力3.0 MPa,空速5 h-1,此条件下,二异丙苯转化率和异丙苯选择性分别约为94%和98%;苯与重芳烃混合液烷基转移反应较适宜的条件为:n(苯)∶n(三异丙苯)=18,反应温度280℃,反应压力3.0 MPa,空速5 h-1,此条件下,三异丙苯转化率、异丙苯选择性和二异丙苯选择性分别约为75%、64%和31%。     

YSBH-4催化剂上苯与丙烯的液相烷基化

采用YSBH-4型分子筛催化剂,在等温积分反应器上分别考察了反应温度、液相空速和苯与丙烯的物质的量之比对苯与丙烯液相烷基化合成异丙苯反应的影响,并基于单因素实验结果设计正交实验,以进一步优化工艺条件。结果表明,YSBH-4催化剂对苯与丙烯液相烷基化合成异丙苯具有良好的催化活性和选择性。适宜的烷基化条件为175℃,液相空速28.52 h~(-1)和苯与丙烯的物质的量比8:1,在该条件下,丙烯转化率为99.76%,烷基化产物中异丙苯、正丙苯、二异丙苯和三异丙苯的选择性分别为85.27%,0.04%,14.61%和1.08%。     

多异丙苯液相烷基转移催化剂MP-02性能研究

在体积50 mL的固定床反应器中考察了反应温度、多异丙苯(三异丙苯和二异丙苯的总称)空速、苯/多异丙苯质量比等工艺参数对液相烷基转移催化剂MP-02反应性能的影响.结果表明,反应温度和多异丙苯转化率存在线性关系,温度越高,多异丙苯转化率越高;降低多异丙苯空速或者提高苯含量,多异丙苯转化率提高;产物中正丙苯含量和反应温度密切相关.随反应温度的提高,正丙苯的相对含量呈指数增加.生成正丙苯的活化能高于生成异丙苯的活化能,因此,高温有利于正丙苯的生成.     

酸量的调变对烷基转移催化剂性能的影响

用小型固定床反应器进行多异丙苯与苯烷基转移催化反应研究,通过改变催化剂载体拟薄水铝石(SB粉)加入量调变其酸量,并进行NH3-TPD和活性评价,结果表明:质量分数10%的SB粉HMCM-49/Hβ分子筛催化剂用于多异丙苯与苯烷基转移较为适宜。在180℃,总液空速为1.4～1.6h-1条件下,二异丙苯转化率达到60%以上,三异丙苯转化率达到50%以上。     

醇酮蒸馏系统模拟优化技术

一、技术简介:本技术采用分子筛催化剂催化苯和丙烯合成异丙苯,异丙苯是制备苯酚丙酮的重要中间体原料,也是航空煤油的重要添加剂,使用本技术合成异丙苯,     

MCM-49纳米分子筛催化剂研制成功

由中国石油吉林石化研究院研制的MCM-49纳米分子筛催化剂成功应用于中国石油吉林石化染料厂苯酚丙酮生产装置,该装置过去一直存在反应温度高、苯烯物质的量比高及需热苯洗频繁等问题,导致异丙苯生产的能耗高,成本居高不下。MCM-49纳米分子筛催化剂的研制成功,解决了以上问题。     

沸石液相烃化合成异丙苯中烷基转移技术进展

多异丙苯烷基转移是苯与丙烯烃化合成异丙苯工艺的重要组成部分。本文介绍了工业化沸石液相烃化中烷基转移技术的特点, 综述了多异丙苯烷基转移催化剂的研究进展, 总结了多异丙苯烷基转移反应的基础研究, 以期对研制高活性催化剂、提高选择性、抑制正丙苯生成、延长催化剂使用寿命等有所裨益, 使沸石液相烃化技术更具竞争力。     

木器高光面漆用丙烯酸酯树脂的制备与性能研究

以甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)为主单体,多种交联体系为功能单体,采用水性固体丙烯酸树脂(SR-675、QZ-7001、QZ-7002)和聚合型乳化剂NRS-10搭配作为体系的表面活性剂,通过预乳化半连续乳液聚合工艺合成了木器高光面漆用丙烯酸酯树脂。探究了水性固体丙烯酸树脂酸值、T_g、相对分子质量以及用量;NRS-10用量、引发剂(APS)用量和树脂T_g对树脂及涂膜性能的影响。结果表明:当采用水性固体丙烯酸树脂SR-675且用量占单体总量的20%(下同)、NRS-10占0.5%、APS占0.75%,树脂T_g设计为40 ℃时,合成的丙烯酸酯树脂制备成木器面漆,涂膜光泽高、附着力好、耐水性好,铅笔硬度可达2H。     

沉淀型Fe-Mn工业催化剂的F-T反应性能

在积分固定床反应器中系统考察了用于Fischer-Tropsch(F-T)合成的沉淀型Fe-Mn工业催化剂的性能.首先对催化剂进行了2000h的稳定性测试,然后在不同反应温度、原料气H₂/CO比、空速和总压下考察其反应性能.结果表明,在2000h的运行过程中,该催化剂活性和选择性较平稳,失活速率较小,且在较高的反应温度下失活速率更小,显示出该催化剂具有良好的长期稳定性;经2000h的运行后,该催化剂仍表现出较高的反应活性和稳定性,同时,还保持着较高的低碳烯烃和C₅₊选择性.此外,当反应条件在一定范围内发生变化时,低碳烯烃和C₅₊选择性变化不大,说明该催化剂具有良好的可操作性.     

Ethylene polymerization with hafnocene adamantolate/MAO system

Summary A new alcoholate of cyclopentadienyl metallocene with voluminous group as ligand substituting chlorine atoms and formula Cp₂Hf(OMAd)₂ (where Cp = cyclopentadienyl and OMAd = derived of 2-methyl-2-adamantol) was synthesized and employed as catalyst for olefin polymerization. The compound was evaluated in ethylene polymerization activated by methylaluminoxane (MAO) using several experimental conditions. These conditions were determined by a statistic method, and a model for dependent variables like catalyst activity and average molecular weight of polymers were developed. The hafnocene alcoholate produced polyethylenes with molecular weights in the same range of the corresponding metallocene dichloride. The new catalyst system showed high stability under temperature of 100°C. In the presence of H₂ as molecular weight controlling agent, the catalyst showed a maximum of activity in the concentration range used. Received: 10 March 2000/Revised version: 13 September 2000/Accepted: 13 September 2000     

More on the poly(L‐lactide) prepared using ferrous acetate as catalyst

Polylactides were prepared by ring‐opening polymerization (ROP) in bulk using as catalyst either stannous 2‐ethylhexanoate at a monomer to catalyst ratio of 2000, or ferrous acetate (Fe(OAc)₂) at monomer to catalyst ratios of 500, 1000, 2000 and 3000. The crystallization behaviour was studied for the prepared polymers as well as the degradation behaviour both in laboratory and natural compost environments by using differential scanning calorimetry, size exclusion chromatography, X‐ray diffractiometry and microscopy. No differences were apparent due to the choice or amount of catalyst used, except for those which could be related to the increased racemization when the Fe(OAc)₂ was used. Copyright © 2004 Society of Chemical Industry     

Effects of in situ esterification on the performance of carboxyl functionalized rubber‐modified epoxy film adhesives

Epoxy‐based film adhesive formulations were developed with 10 wt % solid carboxyl functional rubber. Due to the high rubber content and resulting viscosity restrictions, the rubber could not be prereacted with the epoxy before hot‐melt filming. Therefore, an esterification catalyst was used to perform this reaction in situ before the epoxy curing reactions. The performance of this adhesive system is compared to that of one without the esterification catalyst. A significant difference in the flow characteristics was observed with incorporation of the esterification catalyst, but only small variations in mechanical performance were found. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 728–734, 2000     

Fatty methyl ester hydrogenation to fatty alcohol part II: Process issues

Fatty alcohols are produced by hydrogenating fatty methyl esters in slurry phase in the presence of copper chromite catalyst at temperatures of 250–300°C and hydrogen pressures of 2000–3000 psi. The fatty methyl ester, catalyst, and hydrogen are fed to the reactor cocurrently. The product slurry is passed through gas-liquid separators and then through a continuous filtration system for removal of the catalyst. A portion of the used catalyst in crude alcohol is recycled to the hydrogenator. The overall efficiency of the process depends upon the intrinsic activity, life, and filterability of the catalyst. The fatty alcohol producer therefore requires a catalyst with high activity, long life, and good separation properties. The main goal of the present laboratory investigation was to develop a superior copper chromite catalyst for the slurry-phase process. Two copper chromite catalysts, prepared by different procedures, were tested for methyl ester hydrogenolysis activity, reusability, and filtration characteristics. The reaction was carried out in a batch autoclave at 280°C and 2000–3000 psi hydrogen pressure. The reaction rates were calculated by assuming a kinetic mechanism that was first-order in methyl ester concentration. The catalyst with the narrower particle size distribution was 30% more active, filtered faster, and maintained activity for several more uses than the catalyst with the broader particle size distribution. X-ray photoelectron spectroscopy data showed higher surface copper concentrations for the former catalyst.     

Triphase catalysis: Hydroxylation of cyclo‐octane by NaOCl catalyzed by coordinatively bound manganese(III) porphyrin to nitrogen‐based polymer supports

The anionic manganese (III) porphyrin was immobilized onto crosslinked poly(benzylpicoline‐co‐styrene) resin through coordinate linkage. The immobilized metalloporphyrin was employed as a heterogeneous catalyst for the hydroxylation of cyclo‐octane by NaOCl. The observed reaction rates depend on experimental parameters such as stirring speed, substrate amount, temperature, and catalyst amount. The influence of different polymer‐based axial ligands, particle size, and percent crosslinking of the polymer support was also discussed. The imidazole‐based polymer supports show higher rate constant values than the pyridine‐based supports. The catalyst shows significant decrease in catalytic activity on recycling. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 104–111, 2000     

SAC-2000和SANC-08丙烯腈催化剂混装研究及应用

通过实验室Φ3.8 cm丙烯腈流化床反应器混装研究,优化出了在本体SAC-2000催化剂中混装20%SANC-08催化剂方案。将其应用于齐鲁石化公司4万t/a丙烯腈装置,半年的运行结果表明:混装后丙烯腈单收比混装前提高了1.45%,2.5个月就可收回催化剂成本,半年增加净利润583.89万元。     

Asymmetric Bio-oxidation Using Resting Cells of Rhodococcus rhodochrous ATCC 4276 Mutant QZ-3 for Preparation of (S)-Omeprazole in a Chloroform–Water Biphasic System Using Response Surface Methodology

(S)-Omeprazole is a very effective anti-ulcer medicine that is difficult to be prepared using whole cells at elevated substrate concentrations. In the chloroform–water biphasic system, resting cells of the mutant QZ-3 of Rhodococcus rhodochrous (R. rhodochrous) ATCC 4276 were used to catalyze the bio-oxidation of omeprazole sulfide for preparation of (S)-omeprazole. Using response surface methodology (RSM), the reaction was optimized to work at a substrate concentration of 180 mM and a cell concentration of 100 g/L. The optimal yield of (S)-omeprazole obtained was 92.9% with enantiomeric excess (ee) (>?99%), and no sulfone by-product was detected under the optimal working conditions; reaction temperature 37 °C, pH 7.3 and reaction time, 43 h. A quadratic polynomial model was established, which predicts the experimental data with very high accuracy (R²?=?0.9990). The chloroform–water biphasic system may contribute to the significant improvement in substrate tolerance because almost all substrates are partitioned in the organic phase (water solubility of omeprazole sulfide is only about 0.5 mg/mL), resulting in little damage and inhibition to cells by substrates. The mutant QZ-3 of R. rhodochrous ATCC 4276 exhibited high enantioselectivity, activity and substrate and product tolerance. The aerated flask provides enough oxygen for a high concentration of cells. Accordingly, bio-oxidation is thus more promising for efficient preparation of chiral sulfoxides.

     

加氢还原法制备邻氯苯胺的研究

在2000mL高压反应釜中,采用自制纳米级Ru/PC催化剂进行邻硝基氯苯加氢制备邻氯苯胺。考察了溶剂、温度、压力等工艺参数对加氢的影响。优化的工艺条件:温度100℃、压力1.5~2.0MPa、溶剂甲醇1000mL、邻硝基氯苯500g、催化剂25g、双氰胺5g。在该条件下,邻硝基氯苯转化率为99.8%,邻氯苯胺选择性为96.5%,脱氯率小于1%。催化剂寿命考察16次,活性不减。