甲苯歧化催化剂的中型放大试验——碳九芳烃的综合利用

1977年底复旦大学与湖南省长岭炼油厂共同协作,在长岭炼油厂铂重整车间20公升反应装置上进行了甲苯歧化催化剂中型放大试验。催化剂在重整氢条件下,连续运转1000小时,活性和稳定性良好,苯和二甲苯单程收率始终保持在45%(重)左右,结果详见文献。在此基础上,今年在同一装置上进行了甲苯添加碳九芳烃烷基转移反应中型试验,亦得到了十分满意的结果。当甲苯中加入约40%碳九芳烃     

重整重芳烃选择加氢Ni-M/Al_2O_3催化剂性能

为提高镍基催化剂对萘系化合物的加氢活性和单环芳烃的收率,本研究以Al_2O_3为载体采用浸渍法制备了不同金属助剂修饰的系列Ni-M/Al_2O_3加氢催化剂,对催化剂的物性结构和形貌进行了表征,并考察了其在重整重芳烃中萘系化合物的加氢反应性能。结果表明,含Cu助剂的催化剂具有较佳的织构性能,金属活性组分高度分散,在C_(10)~+重芳烃加氢中具有良好的反应选择性和活性。在反应温度为140℃,压力为1.5 MPa,氢油体积比为300,新鲜油体积空速为1.0 h~(-1)的条件下,萘的转化率和四氢萘的选择性分别达到98%和99%,反应1 000 h稳定性良好。     

吉化炼油厂调整联合芳烃装置的歧化反应进料组成提高收率

吉化炼油厂为进一步节能挖潜,不断优化工艺参数,调整了联合芳烃装置的歧化反应的进料组成,取得较好的效果。歧化反应进料组成对催化剂影响很大,原设计中G：民一66：34,随着600‘的调整操作,Q芳烃量逐渐变大,为了使催化剂活性保持最佳状态,在反应进料负荷为110％的情况下,装置调整了氢油比、反应温度等操作参数,使反应总转化率仍可达到40％－42％,C。芳烃的转化率达到了65％－66％,提高了“四苯”收率。吉化炼油厂调整联合芳烃装置的歧化反应进料组成提高收率     

柴油加氢精制催化剂的研究

研制了以改性氧化铝为载体、以钨镍为活性组元的柴油深度脱芳烃加氢精制催化剂,通过了活性稳定性试验.利用该催化剂,以大庆石化公司炼油厂V(重油催化轻柴油)V(焦化柴油)=41的混合油为原料,在氢分压8.5 MPa、氢油体积比3001、体积空速1.0 h-1和反应温度340℃的工艺条件下,可生产硫质量分数＜30μg·g-1、芳烃体积分数＜10%的清洁柴油.     

不同芳烃质量分数催化柴油加氢裂化产品性质预测

采用FRIPP研制的加氢精制催化剂和轻油型加氢裂化催化剂体系,在中型加氢裂化试验装置上,以高芳烃质量分数催化柴油为原料进行了中试试验,研究了精制催化柴油不同的芳烃质量分数与加氢裂化产品性质变化规律,并预测了不同的芳烃质量分数精制催化柴油加氢裂化产品的性质.结果表明:在裂化催化剂体积空速1.5 h-1、反应总压8.0 MPa、氢油体积比800:1等工艺条件下,随着精制催化柴油芳烃质量分数的提高,汽油馏分产品收率明显降低,而柴油馏分产品收率明显提高,化学氢耗明显降低,汽油馏分芳烃质量分数和辛烷值都明显提高,柴油馏分凝点升高,柴油馏分十六烷指数降低.以此数据建立了六级总动力学模型,实现了汽油馏分产品收率、柴油馏分产品收率、加氢裂化反应化学氢耗、汽油馏分芳烃质量分数、汽油馏分辛烷值、柴油馏分凝点和柴油馏分十六烷指数等产品性质的预测.通过对模型参数的调整,该模型较好地预测了不同芳烃质量分数精制催化柴油加氢裂化产品的性质,预测误差均在5％以内.     

重整重芳烃催化加氢裂解反应工艺条件的探究

以Ptm/ZSM-5为催化剂,重整重芳烃与氢气为原料,在固定床反应器中系统地考察了反应温度、H2/油体积比、反应系统压力以及空速对重整重芳烃加氢裂解反应的影响规律,确定催化剂较优运行条件为:入口温度380℃,反应压力2.8 MPa,氢油体积比为500,重芳烃重时空速(WHSV)为2.0h-1.在此反应条件下,C9转化率...     

芳烃催化加氢反应机理的研究进展

对萘、菲、蒽及芘根据不同计算方法所得的反应活性位进行总结,对苯在金属表面的催化加氢机理-芳烃交换机理进行概括,对菲在MoS₂/Al₂O₃催化剂表面生成二氢菲的基元反应步骤和在Ni-MoS₂/Al₂O₃催化剂表面加氢生成四氢菲的过程进行总结,还给出了蒽的催化加氢反应网络图,分析了在不同催化条件下蒽是否有中环断裂情况的发生,给出了芘在RaneyNickel（W-7）催化剂表面生成二氢芘、四氢芘和六氢芘的催化加氢机理反应图,以及根据能量最低理论,判断芘发生加氢反应的优先位置情况,分别计算了芘加氢生成二氢芘、四氢芘、六氢芘和十氢芘可能存在的加氢路径。并总结了蒽、菲等多环芳烃发生催化加氢反应的规律。加深对多环芳烃催化加氢机理的研究将更好地指导重质油轻质化的进行,因此对多环芳烃催化加氢机理的研究具有重要意义。     

低压氢气下粗苯的脱硫精制 第二报

本文报导以低氢浓度气体加氢精制粗笨的实验室研究结果以及以纯氢气体加氢精制粗笨的中型工厂扩大试验的结果。在以低浓度氢气加氢精制粗笨的实验室研究中,找出了克服结焦的试验流程,考察了过程变数对粗笨脱硫及烯烃饱和反应的影响;比较了不同来源的粗笨的反应性能。通过上述试验找到了获得含硫0.01％及溴价0.5以下的产品的条件。参照所选样的条件,在装有200毫升催化剂的较大反应装置中顺利运转了200小时,油收率98.7%,苯符合合成级规格。 其后在装有9升催化剂的中型工厂中进行了扩大试验。试验表明,以纯氢为原料,在压力20公斤/厘米~2、温度380℃、空速2.0下,生成油溴价及含硫量分别在0.4及0.01％以下,基本上重复了试验室的结果,收率平均为98.2%,产品符合合成级规格。     

分子筛负载铂催化剂上四氢萘加氢裂解反应行为

四氢萘是多环芳烃加氢转化的产物或者中间体,其加氢裂解行为和规律的研究在重芳烃转化和脱除领域有着重要的意义。采用等体积浸渍法制备得到了氧化铝负载贵金属(Pt,Ir和Pd)催化剂和酸性分子筛(MOR和ZSM-5)负载铂双功能催化剂,考察了它们催化四氢萘加氢裂解的反应行为。氧化铝为载体时金属催化剂表面主要发生加氢及脱氢反应,其中金属Pt表现出最高的加氢和脱氢活性。双功能催化剂上四氢萘发生加氢裂化、异构化、氢转移及烷基化等复杂反应,金属Pt通过氢溢流作用提高了分子筛Br?nsted酸活性从而提高催化剂加氢裂解活性和选择性,但过量金属Pt会加剧苯环加氢而不利于单环芳烃的生成。分子筛孔道的限域作用对四氢萘的反应活性及产物分布有重要影响,相比Pt/ZSM-5催化剂,Pt/MOR表现出更高的裂解活性及异构化选择性。Pt/MOR催化剂上四氢萘加氢裂解主要通过异构-裂解路径进行,异构化活性及异构体构型决定了裂解活性及产物的分布。     

UV固化丙烯酸酯改性硅油的合成及性能

以甲基丙烯酸烯丙酯和含氢硅油为原料,通过硅氢加成反应制得丙烯酸酯改性硅油。采用FT—IR表征了产物结构;研究了反应温度、含氢量、催化剂用量对合成反应的影响,以及紫外光（UV）固化性能。结果表明,最佳反应条件为：含氢硅油的活性氢质量分数0．3％、反应温度85℃、铂催化剂质量分数为3×10^-6。产物具有UV固化活性,指干法测定固化时间45s。     

加氢饱和C_(10)~+重芳烃的轻质化反应工艺考察

随着C_(10)~+重芳烃的产量大幅上升,对C_(10)~+重芳烃的有效转化利用技术需求日益迫切,开发了一种将加氢饱和C_(10)~+重芳烃转化为轻质芳烃的高效轻质化催化剂及工艺。采用气相色谱和全二维色谱对加氢饱和C_(10)~+重芳烃进行了组分分析,研究了反应温度、氢气压力、质量空速、氢油比等工艺条件对轻质化的转化率和选择性等结果的影响,以及催化剂的长周期稳定性和再生性能。在考评温度380℃,氢气压力5.0MPa,液体质量空速1.5 h~(-1),氢油体积比1 000的条件下,C_(10)~+的转化率达到75%以上,轻质芳烃,包括苯、甲苯、二甲苯、C_9和C_(10)的选择性65%左右,得到的轻质化产品中,苯、甲苯和二甲苯(BTX)的占比达到75%以上,苯产品纯度大于98%,二甲苯纯度大于99.2%。研究表明,所用的轻质化催化剂具有良好的长周期稳定性,在300 h的连续反应中,C_(10)~+的转化率和轻质芳烃,包括BTX,C_9和C_(10)的选择性保持稳定。长周期运行后失活的催化剂经过简单的焙烧可以再生,再生催化剂的活性与新鲜催化剂的活性相当。将加氢饱和和轻质化技术进行耦合,从C_(10)~+重芳烃生产轻质芳烃,能够极大地提高C_(10)~+重芳烃的利用价值,具有很好的技术可行性和工业应用前景。     

年产百吨级二氟甲烷制备技术

该项目采用自行创制的催化剂对二氯甲烷进行加压循环气相氟化反应制备二氟甲烷。二氯甲烷转化为:二氟甲烷的选择性高达99.9％,产品纯度达到99.8％,催化剂可多次再生,且再生后活性仍较高。研究中对反应参数进行了优化,与国外工艺不同,该工艺选用了较低的反应温度、MHF/MR30及较短的停留时间。项目完成了二氟甲烷的百吨级中试研究,为加快产业化进程,进行2000t/a工业化试验是今后的研究方向。     

Oxidation of Methyl Aromatics and Hetero Aromatics to Their Corresponding Aldehydes

The direct partial oxidation of methyl aromatics and hetero aromatics to their corresponding aldehydes strongly depends on nature, strength and concentration of acidic and basic surface sites of the catalysts, the acid-base properties of the reaction mixture and, additionally, on the electronic properties, i.e. nucleophilicity of the reactants. The increase of catalyst basicity by addition of alkali cations as well as the entire reaction mixture basicity by co-feeding of pyridine lead to dramatic improved aldehyde selectivities.     

Dynamic modelling of a gas phase catalytic fixed-bed reactor—I: Experimental apparatus and determination of reaction kinetics

A large scale fixed bed pilot reactor for performing dynamic experiments is described. The reactor system is especially designed to suppress secondary dispersion effects not characteristic for the packed bed itself.As a model reaction the reaction between oxygen (<1%) and hydrogen on a platinum catalyst supported by alumina has been used.Differential reactor experiments disclosed a hysteresis phenomenon in the catalyst activity. The catalyst is generally more active when going from high to low temperatures than vice versa.A global first order reaction rate expression with Arrhenius temperature dependency fits the fixed-bed reactor profiles well but the static gains badly. However by simultaneous estimation of frequency factor and activation energy in several axial segments a much better approximation to the static gains was obtained. This result indicates that the reaction kinetics is more complicated than first assumed. However for dynamic modelling the exact reaction mechanism is not needed.     

固定床渣油加氢过程催化剂级配优化研究及工业应用

采用SHIFT—G反向催化剂级配技术对固定床渣油加氢催化剂级配进行优化,中型试验和工业应用结果表明,优化装填后的催化剂级配体系消除了影响装置操作周期的不利因素,合理地分配了反应负荷,有效地改善了加氢产品性质,延长了工业装置运转周期,提高了经济效益。     

Scale Continuous Microwave Dry‐Media Reactor – Part II: Application to Waxy Esters Production

The solvent free esterification reaction between stearic acid and stearyl alcohol has been examined with a montmorillonite clay as catalyst. To aim for industrial application the system has been studied on reaction rate, product purity, catalyst behavior and water removal as function of the process conditions. To avoid an etherification side reaction and to aim for the highest reaction rate, the temperature should be strictly maintained at 170 °C. This is provided on larger scale by the application of microwave heating. Although the examined Brønsted acid clay was found to lose its catalytic activity at very low water activities, a yield of 95 % pure stearyl stearate can be obtained by simply filtering of the clay without solvent extraction or distillation. The “waxy” esterification reaction was investigated with the pilot plant continuous microwave dry‐media reactor (CMDR). The reaction time needed for 95 % yield was reduced by a factor 20–30 in comparison with industrial conventional reactors. This was due to the more homogeneous heat transfer of microwaves, which allows to reach a higher bulk temperature.     

A6型氨合成催化剂还原条件的研究 Ⅰ.还原温度对还原过程、催化剂结构和活性的影响

在常压、温度435℃到530℃的条件下研究了A6型氨合成催化剂的还原。发现温度低于515℃时,A6型催化剂不可能全部还原,而只可能达到一个极限还原度。相应于435℃、490℃和515℃时的极限还原度是22％、82％和100％。 X光结构分析表明,未还原的催化剂是尖晶石结构,还原后是α-Fe。愈难还原的尖晶石部分其晶胞参数愈小。 在300大气压下对不同还原度的样品进行了活性试验,用T方程计算了反应速度常数。发现催化剂愈难还原的部分经还原后其比活性愈高。     

Development and introduction of a highly efficient catalyst for the butane–butylene fraction oligomerization process for the production of a high-octane automobile gasoline compound

The main stages in developing a technology for the production of high-silica ZSM-5 zeolite-based catalyst for the butane–butylene fraction (BBF) oligomerization process are described. The application of a new zeolite surface modification procedure allows the attainment of higher selectivity and target product yields (compared to familiar analogs) and the synthesis of more branched (and thus more high-octane) oligomers at lower pressures. The introduction of promoting metal Ga raises the target gasoline fraction yield by 0.9%, compared to the unpromoted catalyst. Comparative pilot tests of industrial (BAK-70U) and the developed (Ga-ZSM-5/Al₂O₃) BBF oligomerization catalysts are performed under the following conditions: pressure, 1.5 MPa; initial working temperature, 300°C; feedstock hourly space velocity (FHSV), 1.5 mL BBF/(mL cat h). It is shown that using modified ZSM-5 based catalyst results in a gasoline fraction yield 7% higher than with BAK-70U. The higher quality of the oligomerizate obtained on Ga-ZSM-5/Al₂O₃ is observed throughout the period of tests (191 h): MON is 2 points higher, and the concentration of gums is 50% lower. The results from these studies and tests are used for the development and industrial implementation of a technology for the production of the KOB-1 zeolite oligomerization catalyst: 2.5 t of industrial catalyst has been produced by September of 2016 at the industrial facilities of ZAO Redkino Catalyst Plant. The next important stage in the implementation of the Gazprom Netf innovative development strategy in oil refining is a pilot run of the new oligomerization catalyst in the combined industrial MTBE–oligomerizate production plant of Gazprom Neft Moscow Oil Refinery. The introduction of the KOB-1 catalyst at the Gazprom Neft Oil Refinery will be an important step in improving the efficiency of technologies for the production of high-margin products, especially compounds of commercial automobile gasoline.     

Development of solid base catalyst X/Y/MgO/-AlO for optimization of preparation of biodiesel from L.seed oil

The preparation and regeneration conditions of the identified catalyst X/Y/MgO/?-Al₂O₃ with high catalytic activity were studied and optimized. The biodiesel was prepared by transesterification of Jatropha curcas seed oil produced in Guizhou with methanol at its reflux temoerature in the presence of X/Y/MgO/?-Al₂O_{3 .} The pilot plant tests were carried out in a 100 L reaction vessel. Both average yield and fatty acid methyl esters (FAME) content reached more than 96.50% under the optimum reaction conditions of the pilot plant tests designed with an oil/methanol molar ratio of 1 : 10, catalyst concentration of 1.00%, and reaction time of 3 h at reflux temperature. In addition, analysis shows that the quality of biodiesel meets the standard EN 14214.     

高比例二甲胺分子筛催化剂

以丝光沸石为原料,经预处理、离子交换等过程,制得合成甲胺催化剂。这些处理过程有效地调节了丝光沸石的表面酸性和孔结构。该催化剂用于甲醇氨化制甲胺过程中,可以提高二甲胺选择性,催化剂的性能达到国际同类产品先进水平,并已完成中试,为现有甲胺生产装置的改造提供了一种新型的高性能催化剂。