SAPO-18分子筛在丁烯裂解中的应用

选用磷源、硅源、铝源、去离子水以及有机模板剂作为原料,采用水热合成法制备了SAPO-18分子筛。采用XRD、SEM和BET表征手段对分子筛进行了特性分析,考察了SAPO-18分子筛在丁烯裂解催化反应中的催化性能。SAPO-18分子筛初期催化效果比较稳定,很好的控制了催化反应中氢转移副反应的发生,并且得到了较高的丙烯收率。     

1-丁烯催化裂解制丙烯和乙烯反应性能的研究

以MCM-49分子筛为催化剂,纯1-丁烯为原料,考察了反应压力和空速对烯烃催化裂解制丙烯,乙烯反应性能的影响.选择适宜的反应压力和空速条件能够有效地抑制副反应,从而提高丙烯,乙烯的总产率。     

不同模板剂合成的SAPO-34分子筛催化丁烯裂解

受下游产品的影响,丙烯需求量逐年上升,提高丙烯生产能力显得尤为重要。SAPO-34分子筛具有八元环孔道结构,在丁烯裂解中可有效提高低碳烯烃选择性,尤其是丙烯选择性。以二乙胺、四乙基氢氧化铵和二乙胺+四乙基氢氧化铵为模板剂合成SAPO-34分子筛,采用XRD、NH3-TPD和SEM等进行表征,并在固定床反应器上考察模板剂对分子筛催化性能的影响。结果表明,模板剂种类对制备的SAPO-34分子筛的晶粒大小、酸强度、酸量以及催化性能有重要影响。以四乙基氢氧化铵为模板剂合成的分子筛酸量最少,酸性最弱;以二乙胺为模板剂合成的分子筛酸量最大且酸性最强,双模板剂发挥加和效应。将SAPO-34分子筛用于丁烯裂解反应时,酸量越少,酸性越弱,丙烯收率越高,丙烯最高收率为33.61%。     

碳五烃催化裂解制取丙烯/乙烯反应性能

以ZSM-5分子筛为催化剂,碳五烃混合物为裂解原料,考察空速对碳五烃催化裂解制丙烯/乙烯反应性能的影响。结果表明,在580℃和实验空速范围,随着空速的增加,碳五烷烃及烯烃转化率整体呈下降趋势,但碳五烯烃转化率远高于碳五烷烃。乙烯及丙烯收率在空速3 h-1时达到最大,分别为10.51%和13.02%。碳四烯烃收率随空速的升高而降低,但各丁烯异构体相对于总烯烃的质量分布接近热力学平衡态。     

硅源对ZSM-5分子筛合成和催化性能的影响

为了考察硅源对ZSM-5分子筛合成和催化性能的影响,分别采用白炭黑、硅胶、硅溶胶和单分散SiO₂为硅源合成ZSM-5分子筛,对合成的ZSM-5分子筛进行XRD、SEM、BET和NH₃-TPD表征,并以C₄烯烃为原料评价合成的ZSM-5分子筛的催化裂解性能。结果表明,以硅溶胶为硅源合成的ZSM-5分子筛具有较好的结晶度和催化活性。水热处理使分子筛酸量减少,孔容缩小,改善了分子筛的乙烯丙烯选择性。经600 ℃水热处理4 h的ZSM-5分子筛在常压、580 ℃和空速9 h^-1反应条件下,丁烯催化裂解为乙烯和丙烯平均转化率为90.2%,乙烯和丙烯总收率达61.1%。     

双模板剂调控SAPO-34对1-丁烯催化裂解的影响

利用水热合成法,通过调控模板剂吗啡啉和四乙基氢氧化铵物质的量比[n(MOR)∶n(TEAOH)]合成出不同SAPO-34分子筛。采用XRD、SEM、NH₃-TPD等测试方法对合成样品进行表征,并考察其在1-丁烯催化裂解制丙烯反应中的催化性能。结果表明,双模板剂相比单模板剂制得的SAPO-34分子筛具有不同的酸性和颗粒尺寸,适宜的[n(MOR)∶n(TEAOH)]可以协同SAPO-34分子筛有更弱的酸强度和B酸酸位,从而抑制裂解过程中氢转移反应的发生。当n(MOR)∶n(TEAOH)=2.0∶0.5时可以最大程度的提升丙烯产率和选择性,在1-丁烯催化裂解制丙烯中具有最高的丙烯产率和丙烯选择性,分别为37.03%和45.78%,可以有效应用于1-丁烯催化裂解反应。     

碳五烃催化裂解制取低碳烯烃反应性能及机理

以ZSM-5分子筛为催化剂,碳五烃混合物为裂解原料,考察温度及稀释比对碳五烃催化裂解制丙烯/乙烯反应性能的影响。结果表明:随温度升高碳五烷烃及烯烃的转化率均不断升高,但碳五烯烃的转化率远高于碳五烷烃的转化率。同时乙烯及丙烯的收率也随温度的升高而升高,空速3.06 h-1,分压23.24 k Pa时,分别由450℃的2.38%,8.84%升高到620℃时的13.86%和19.67%。另外,随稀释比的增加,碳五烯烃转化率,乙烯、丙烯及丁烯的收率不断下降,但C6烃的收率随稀释比的增加而升高。碳五烯烃催化裂解机理分析指出:碳五烯烃催化裂解过程中碳五烯烃在直接裂解生成乙烯和丙烯的同时,也可通过二聚成C10中间体,然后生成的C10中间体再发生顺次裂解反应。该机理应用于实验规律的解释,取得了满意的结果。     

硅源用量对SAPO-18分子筛合成及催化性能的影响

采用水热合成法,以N,N-二异丙基乙胺为模板剂合成SAPO-18分子筛,并用X射线衍射、X射线荧光光谱、扫描电子显微镜、NH3程序升温脱附及N2吸附-脱附等对其结构进行表征,系统研究合成凝胶中硅源用量对SAPO-18分子筛合成及其在甲醇制烯烃反应中催化性能的影响。结果表明,在晶化温度453 K、晶化时间96 h和合成凝胶中0.3≤n(Si O2)∶n(Al2O3)≤1.2条件下,能合成出纯相的SAPO-18分子筛,其中,当n(Si O2)∶n(Al2O3)=0.6,在反应时间135 min时,合成的SAPO-18分子筛具有较高的双烯选择性(乙烯+丙烯)。合成凝胶中硅源的用量对SAPO-18分子筛酸性有显著影响,适当增加分子筛中强酸比有助于提高乙烯和丙烯选择性,但缩短催化剂寿命。     

La改性ZSM-5分子筛及其在催化裂解反应中的应用

采用高温水热法和等体积浸渍法将La离子负载于ZSM-5分子筛上得到了改性ZSM-5分子筛材料。水热法La改性样品改变了ZSM-5的晶胞尺寸,提升了其强酸、弱酸及总酸量。浸渍法改性样品也提高了其酸量但是对晶胞参数没有影响。将改性样品应用于正己烷催化裂解反应中,两种方法均得到了较高的双烯收率,其中水热法改性样品在空速为6 h-1时乙烯收率和丙烯收率分别为23.39%和25.17%,这与原样相同空速下的乙烯丙烯收率(乙烯为21.19%,丙烯为21.04%)相比分别提升了约2%和4%,略高于浸渍法改性样品。在长周期反应寿命方面也有了显著提高,在空速为4 h-1时,水热法改性样品(2000 min)和浸渍法改性样品(1600 min)均显著优于原样(800 min)。这些结果表明采用水热法La改性可以更好地提升ZSM-5分子筛在正己烷催化裂解反应中的性能。     

碳四烯烃催化裂解制乙烯和丙烯热力学分析及反应性能考察

以C2~C4烯烃作为碳四烯烃催化裂解制乙烯和丙烯反应系统模型,借助吉布斯自由能最小原理对碳四烯烃裂解过程进行热力学计算。结果表明,随着温度升高,乙烯平衡收率升高,610℃时,丙烯平衡收率达44.8%。在丁烯裂解过程中,随着压力降低,乙烯平衡收率升高,压力低于0.1 MPa时,随着压力降低,乙烯平衡收率升高速率加快,由0.1 MPa时的21.8%升至0.01 MPa时的46.5%。压力在(0.05~0.8)MPa时,随着压力降低,丙烯平衡收率缓慢升高,0.05 MPa时达45%,之后迅速下降。热力学计算结果与实验结果比较显示,实验温度范围,1-丁烯在ZSM-5分子筛催化剂上催化裂解过程中乙烯和丙烯的收率以及丁烯转化率随温度的变化趋势同热力学计算结果一致。从提高丙烯收率的角度,建议温度(500~580)℃,压力0.05 MPa。     

The catalytic heat exchanger using catalytic fin tubes

The characteristics of a catalytic heat exchanger which integrates heat generation and heat exchange into one equipment have been investigated by the experiment and numerical simulation. The surface of the fin tubes was catalyzed by the formation of the oxide layer and the subsequent washcoating of ZrO₂, followed by the impregnation of Pd catalyst. The experimental results showed that the performance of catalytic combustion in the catalytic heat exchanger was more significantly affected by the inlet velocity of the mixture than by its inlet temperature and equivalence ratio. It was also found that the catalytic surface area was a critical parameter to obtain the complete conversion of the mixture. Numerical simulation has been performed with a commercial software FLUENT. The calculated results indicated that the performance of the catalytic combustion was influenced by the catalytic fin configuration as well as the flow pattern of the mixture over the catalytic fins. The results recommend that the number and thickness of catalytic fins should be designed above 6 pieces/inch and less than to achieve the best performance in the catalytic heat exchanger.     

一种新催化体系的构建及其催化活性研究

用一种配体(5,5,7,12,12,14-六甲基-1,4,8,11-四氮杂环十四烷-N'-乙酸)和镧离子(Ⅲ)构建了一种新的催化体系,并用于催化对硝基苯酚磷酸二酯(BNPP)水解裂解。利用紫外-可见分光光度法研究了BNPP的催化水解的动力学。实验结果表明:这种新催化体系与其他相似的镧离子体系相比表现出更高的活性、水溶性和稳定性,在这一体系作用下,BNPP催化水解的速率比其自水解的速率提高了107倍左右。光谱分析表明,催化体系的活性物种是由镧离子和配体构成的大环配合物。     

Other catalytic properties

The behavior of fresh and aged EUROCAT V₂O₅–WO₃/TiO₂ SCR catalysts in the (I) oxidative dehydrogenation of light alkanes, and conversion of (ii) propan-2-ol, (iii) NO in the presence of propene and oxygen, (iv) propane and propene and (v) chloropropane is reported to analyse possible modifications of the catalyst properties during use and give a more comprehensive general picture of its surface and reactivity properties.     

Exhaustive catalytic hydrodechlorination

To develop technology for the utilization of waste from vinyl chloride production by the method of catalytic hydrodechlorination, the main aspects of kinetics are studied, which makes it possible to describe the process of exhaustive catalytic hydrodechlorination on a Pd/γ-Al₂O₃ catalyst. Conditions are determined that provide stable work of the catalyst and the complete extraction of chlorine from waste: excess hydrogen of ∼270°C and a contact time of 10–15 s. The process does not require high pressure. The rate of chlorinated hydrocarbon consumption in the process of hydrodechlorination of the main components of waste (1,2-dichloroethane, 1,1,2-trichloroethane, and tetrachloroethylene) is measured at 200–270°C. Mathematical equations for simulations of the hydrodechlorination reactor unit are obtained. The results can be used to develop an experimental pilot plant.     

乙炔氢氯化制备氯乙烯的非汞催化技术研究

介绍了非汞催化乙炔氢氯化制备氯乙烯的研究状况、催化剂性能、反应技术等,并指出了今后非汞催化乙炔氢氯化制备氯乙烯的研究重点和研究方向。     

Axial characterization of catalytic activity in close-coupled lightoff and underfloor catalytic converters

A exhaust system consisting of a close-coupled Pd technology 32 in³ lightoff converter and Pt/Rh technology 170 in³ underfloor converter was vehicle-aged for 56000 miles on a vehicle equipped with a 3.8 l engine. Following this aging, the converters were taken off the vehicle and cut into 1″ thick sections along their axis and characterized for lightoff and warmed-up activity using a laboratory reactor to simulate vehicle exhaust. Each section was also analyzed for the quantity of oil additive poisons (phosphorus and zinc) deposited. Following this initial characterization, the phosphorus and zinc deposits were removed, and the sections were characterized again for lightoff and warmed-up activity. This procedure was used to qualitatively determine the relative contribution of oil additive poisoning and thermal sintering to the total activity deterioration as a function of axial position in the catalyst monoliths.

Analysis of the lightoff converter as taken from the vehicle showed a dramatic axial gradient in the lean and stoichiometric lightoff and warmed-up (600°C) performance for HC, CO and NO_x, with most of the deterioration having taken place in the forward-most 1″ section of the converter, which was consistent with the gradient in the deposition of phosphorus (P) and zinc (Zn) in this converter. Comparison of these data sets with those obtained after removal of the P and Zn poisons indicates that most of the total deterioration of lean HC and CO activity can be attributed to P and Zn poisoning of the forwardmost 1″ section. When tested under stoichiometric conditions, most of the deterioration of HC activity is attributable to P and Zn poisoning, while most of the deterioration of CO and NO_x activity is attributable to thermal deterioration. A similar activity and poison deposition gradient was detected in the underfloor converter, but to a smaller extent.     

催化燃烧与催化剂材料在VOCs治理方面研究进展

介绍了VOCs对人类环境和健康造成的危害。概述了工业应用中常用于治理有机废气的催化燃烧技术的基本原理、特点及相关催化剂的研究现状，指出此类催化剂应朝着提高低温活性、热稳定性、抗毒能力和价格低廉的方向发展。     

催化裂化汽油催化氧化及萃取脱硫的研究

以分子氧为氧化剂,将催化氧化与萃取分离相结合,开展催化汽油氧化萃取脱硫研究。结果表明,与直接萃取相比,汽油经过氧化及溶剂萃取,汽油脱硫率有所提高,并且随着氧化温度的提高而增大,氧化过程对催化汽油脱硫有贡献。催化剂能够加速硫化物氧化反应,几种催化剂的汽油脱硫率从大到小顺序为：氧化铈＞碳酸锰或四硼酸钠或氧化锌＞硼酸或过硼酸钠。使用氧化锌或碳酸锰催化剂时,随着催化剂用量的增加,汽油脱硫率总体呈现降低的变化趋势。以硼酸为催化剂时,脱硫率随着催化剂用量的增加先增加后降低,认为催化汽油中硫化物的氧化反应符合连串反应机制。     

催化型多孔陶瓷球制备及催化玉米秸秆热解

针对生物质热解液化过程中生物油品质差的问题,本文以陶瓷球作热载体为研究基础,制备了5种负载金属氧化物（ZnO、NiO、CeO₂、Cr₂O₃、Fe₂O₃）的多孔陶瓷球,在固定床反应器上研究多孔陶瓷球催化剂对玉米秸秆热解过程的催化效果。结果表明：多孔陶瓷球基体在热解过程中有一定催化活性,经浸渍改性处理后,都能促进生物油产率的提高,其中Ni基多孔陶瓷球热解的产率高达41.62%。多孔陶瓷球负载的5种金属氧化物可促使生物油中酚类、呋喃类物质的含量明显增加,酸类物质的含量明显降低,且种类减少,其中CeO₂降酸效果显著,降低幅度为37.15%。此外,催化型多孔陶瓷球的引入促进了不可冷凝气中C _n H _m （n≥2）的生成,烯烃类中乙烯的增长幅度最大,为50.53%,同时生物炭的理化特性在一定程度上得到改善和提高。