中国炼油与石油化工

Select

1. 5A分子筛的晶粒尺寸对其乙烯/乙烷吸附分离性能的影响

边青敏忻睦迪徐广通陈帅邹亢史延强

2019, 21 (4): 36-41.

摘要（468）

PDF（pc）（623KB）（657）

The adsorptive separation of ethylene and ethane exhibits a less energy-intensive -alternative technique with development potential among all separation processes currently. In this approach, zeolite 5A with different particle sizes from 3340 nm to 440 nm was synthesized by in-situ hydrothermal synthesis. The effect of particle size on the adsorptive separation performance of zeolite 5A was investigated. The results show that the accessibility of Ca2+ enhance dramatically with gradually declined particle size. At the initial stage of particle size reduction, the ethylene IAST (Ideal Adsorbed Solution Theory) selectivity of zeolite 5A increased up to 5.6 with reduced diffusion resistance and the strengthened π-complexation. With the further shrunk particle size (< 710 nm), the ethylene IAST selectivity of zeolite 5A deteriorate sharply, which stems from competitive adsorption between ethylene and moisture on Ca2+ adsorption sites.

相关文章 | 多维度评价

Select

2. 硅钨酸酸化的新型MIL-101（Cr）催化剂及其对正庚烷异构化反应的催化性能

张微刘荣江马守涛 Dimitriy Kuvshinov 所艳华汪颖军

中国炼油与石油化工 2022, 24 (1): 68-80.

摘要（412）

PDF（pc）（1596KB）（34）

0.4%Pt/xSTA-MIL-101(Cr) metal-acid bifunctional catalysts were prepared by impregnation using STA-MIL-101(Cr) as the support. The synthesized samples were verified to exhibit a typical octahedral structure of MIL-101(Cr) and the pore structure were arranged orderly. The specific surface area of the samples was extremely high and the samples were micro-mesoporous composite materials. Silicotungstic acid could retain its Keggin structure in the 0.4%Pt/xSTA-MIL-101(Cr) samples and the catalyst possessed moderately strong Br?nsted acid sites. Besides, the dispersion of Pt particles in MIL-101(Cr) was relatively high. n-Heptane isomerization was first used as a probe to test the novel 0.4%Pt/xSTA-MIL-10(Cr) catalyst. Compared with the conventional silicate catalysts, the catalytic performance of 0.4%Pt/30wt%STA-MIL-101(Cr) was significantly improved with n-heptane conversion of 58.93% and iso-heptane selectivity of 95.68%, respectively, when the reaction time was 2 h at the reaction temperature of 260 oC. The catalyst could still maintain a relatively high catalytic performance during the reaction time of 5 h. Compared with the non-noble metal catalysts, the catalytic efficiency is relatively high. The mechanism model of n-heptane isomerization over 0.4%Pt/xSTA-MIL-101(Cr) catalyst was established.

参考文献 | 相关文章 | 多维度评价

Select

3. 石油化工中的结晶

张得江范瑛琦谢丽丁晖殿王皓

中国炼油与石油化工 2021, 23 (2): 1-10.

摘要（369）

PDF（pc）（734KB）（340）

结晶是一种应用广泛的产品精制单元操作。了解石油化工中结晶过程的特点，有助于选择和设计新的结晶工艺。本综述简要介绍了结晶工艺的特点，总结了在石油化工中应用的结晶工艺，讨论了结晶工艺设计中应注意的问题。石油化工工艺中的结晶主要用于聚合物单体的提纯，并且往往是整个精制流程中的一部分。合理的设计一个结晶工艺，需要从全局考虑工艺的安全性、可行性和经济性。

参考文献 | 相关文章 | 多维度评价

Select

4. 工业管式反应器中乙烷蒸汽裂解过程的建模与优化

Mohsin Ali 廖祖维杨遥孙婧元蒋斌波王靖岱阳永荣

2020, 22 (4): 117-125.

摘要（289）

PDF（pc）（639KB）（605）

Ethane steam cracking process in an industrial reactor was investigated. A 1-demsional (1D) steady-state model was developed firstly by using an improved molecular reaction scheme and then simulated in Aspen Plus. A comparison of model results with industrial data and previously reported results showed that the model can predict the process kinetics more accurately. In addition, the validated model was used to study the effects of different process variables, including coil outlet temperature (COT), steam-to-ethane ratio and residence time on ethane conversion, ethylene selectivity, products yields and coking rate. Finally, steady-state optimization was conducted to the operation of industrial reactor. The COT and steam-to-ethane ratio were taken as decision variables to maximize the annual operational profit.

参考文献 | 相关文章 | 多维度评价

Select

5. 高分散的CoWO4或CuWO4提高WO3的光催化性能

何放康明亮宋春冬杨霞张静

2019, 21 (4): 9-20.

摘要（247）

PDF（pc）（1310KB）（738）

本文采用原位浸渍与固相反应结合，成功地合成了CoWO4或CuWO4高度分散在WO3表面的复合CoWO4/WO3或CuWO4/WO3光催化剂。通过XRD，SEM，TEM，EDS，HR-TEM，UV-vis DRS，SPV和活性物种实验研究了CoWO4/WO3和CuWO4/WO3样品的结构，形貌，光物理性质和光催化降解机理。XRD，SEM和TEM结果表明，当CoWO4或CuWO4的负载量较小时，CoWO4或CuWO4高度分散在WO3表面上。但是当CoWO4或CuWO4的负载量增加时，WO3表面的CoWO4或CuWO4颗粒发生明显的团聚。可见光光催化降解RhB的实验结果表明，所有CoWO4/WO3或CuWO4/WO3样品的光催化活性都优于WO3的活性。这主要是因为WO3和CoWO4或CuWO4之间形成的II型异质结能够显著促进光生电子和空穴的分离。此外，CoWO4/WO3和CuWO4/WO3系列样品中，0.2％CoWO4/WO3和0.2％CuWO4/WO3分别显示了最优异的光催化活性，与WO3相比，其光催化活性分别提高了约9.1倍和6.8倍。此外，活性物种实验表明，光催化过程中在0.2％CoWO4/WO3和0.2％CuWO4/WO3催化剂上产生的?OH，h+和?O2?都是光催化降解RhB的活性物种。本文为设计高活性的光催化剂提供了一种思路。

参考文献 | 相关文章 | 多维度评价

Select

6. 萃取精馏与变压精馏分离甲醇-乙腈共沸物的研究

韩东敏陈艳红

2020, 22 (4): 137-146.

摘要（243）

PDF（pc）（1263KB）（592）

In the present work, a comparative study of the extractive distillation and pressure swing distillation for methanol-acetonitrile azeotropic separation is performed for the first time. Different separation alternatives, including the conventional extractive distillation, the extractive distillation with vapor or liquid side-stream, the pressure-swing distillation with or without full heat integration, and the heat-pump assisted pressure-swing distillation are rigorously simulated and optimized based on the minimum total annual cost (TAC) via the sequential iterative strategy. The results show that TAC and CO2 emission of the new extractive distillation with vapor side-stream (Vapor-SED) are similar to that of the extractive distillation with liquid side-stream (Liquid-SED). Furthermore, the Vapor-SED and Liquid-SED gives 30.01% and 30.56% reduction in TAC and 23.32% and 23.49% reduction in CO2 emission, respectively, over the most competitive fully heat-integrated PSD configuration. Hence, extractive distillation with vapor or liquid side-stream appears to be better option economically and environmentally for separation of methanol and acetonitrile.

相关文章 | 多维度评价

Select

7. Insights into the Reaction Network and Mechanism of Green Aerobic Oxidative Esterification of Methacrolein over Different Heterogeneous Catalysts

厉晨豪夏长久刘聿嘉黄开盟彭欣欣刘金胜林民朱斌罗一斌舒兴田

中国炼油与石油化工 2021, 23 (3): 1-11.

摘要（233）

PDF（pc）（848KB）（251）

The oxidative esterification of methacrolein (MAL) is an important way to prepare high-valued methyl methacrylate (MMA), but this process is ultra-complex, due to the highly reactivity of both C=O and C=C bonds within MAL. In order to further improve the selectivity of MMA selectivity, the reaction network and mechanisms over different catalysts have been profoundly investigated in this paper. Five kinds of reactions are involved in this process, including (a) hemiacetal/acetal reaction; (b) aerobic oxidation of aldehyde/alcohol; (c) alkoxylation of C=C double bond; (d) Diels-Alder reaction; (e) hydrogenation reaction of double bond/ carbonyl. Among them, Diels-Alder reaction of MAL is noncatalyzed, and Br?nsted acid sites favor promoting hemiacetal/acetal reaction of MAL with methanol, while alkaline sites enhance the alkoxylation of C=C bond with methanol. In particular, by using Pd-based catalysts, several kinds of hydrogenated products are formed, hence with lower MMA selectivity than those of Au-based catalysts. Notably, it is of necessary to match the hemiacetal reaction of MAL with methanol to and aerobic oxidation of hemiacetal, which is relevant with the amount of Br?nsted acid and redox sites. Consequently, this work provides a good guidance for the further design of both catalysts and processes in future.

参考文献 | 相关文章 | 多维度评价

Select

8. HTS分子筛催化甲苯无有机溶剂条件下的氧化溴化反应研究

彭欣欣夏长久林民朱斌罗一斌舒兴田

2020, 22 (4): 1-9.

摘要（194）

PDF（pc）（877KB）（516）

本文研究了双氧水和溴化氢溶液体系中，空心钛硅分子筛（HTS）催化甲苯在无有机溶剂条件下的氧化溴化反应。在优化的反应条件下，甲苯转化率可达90.7%，一溴甲苯选择性达99.0%。采用UV-Raman光谱对甲苯溴化反应的机理进行了研究。结果表明，HTS分子筛可高效催化溴化氢和双氧水氧化反应并生成大量的活性溴物种，该溴物种可通过亲电取代反应进一步促进甲苯溴代制备一溴甲苯。基于拉曼光谱的研究结果，提出了基于HTS分子筛催化的活性溴物种“产生-存储-反应”的甲苯溴化两步反应机理。

相关文章 | 多维度评价

Select

9. 热集成水网络优化设计的最新进展

张池金任聪静廖祖维孙婧元王靖岱阳永荣

中国炼油与石油化工 2021, 23 (3): 69-75.

摘要（188）

PDF（pc）（577KB）（166）

It is well known that the process industry is an energy-intense and water-consuming industry and is the main source of industrial water consumption and energy in China. Energy integration and mass integration are important approaches to achieve energy saving and emission reduction in the process industry. Generally, the methods can be classified into two groups: conceptual design methods and mathematical programming methods. The former includes mainly graphical methods based on pinch technology that is operated easily. A feasible solution can be quickly obtained. Conceptual design methods are sequential in nature including targeting and design two steps. The latter is based on superstructure optimization and corresponding algorithm is adopted to solve the model. The trade-offs and connections among the entire network can be established and explored. Multiple factors can be considered and optimized simultaneously by mathematical programming methods. This paper describes the synthesis of heat integrated water allocation networks (HIWAN) based on both conceptual design methods and mathematical programming methods systematically. In addition, the characteristics and shortcomings of the existing research methods are summarized, and the future research direction is prospected.

相关文章 | 多维度评价

Select

10. COSMO-SAC模型和密度泛函理论在萃取分离剂分子设计中的应用比较研究

方静王一晶张淑婷郑雯雯李浩李春利

2019, 21 (3): 103-111.

摘要（188）

PDF（pc）（521KB）（718）

基于离子液体的结构可设计性，通过计算机辅助的方式可以设计出具有高萃取效果的离子液体萃取分离剂。通常使用的是COSMO-SC模型和密度泛函理论，两种方法均具有各自的优点。然而，本文发现对于同一待分离体系COSMO-SAC模型和密度泛函理论所预测的萃取效率排序存在不同。针对这一问题，本文以离子液体萃取脱硫为例通过COSMO-SAC模型筛选出具有高分离效率的六种离子液体，同时使用密度泛函理论在机理的角度上获得了六种离子液体的分离效率，发现两种方法的分离效率确实存在不一致。通过实验并利用高效液相色谱对分离后的含硫化合物进行浓度测定，实验结果表明，六种离子液体的分离效率与密度泛函理论的结果是一致的。最终，在计算原理的角度上说明了两种模型计算结果存在差异的原因。

参考文献 | 相关文章 | 多维度评价

Select

11. DIFFUSION AND ADSORPTION OF TETRALIN HYDROCRACKING REACTION ON DIFFERENT ZEOLITES BY MOLECULAR SIMULATION

孙立杰樊亚明董松涛羡策龙湘云李大东

中国炼油与石油化工 2021, 23 (1): 1-9.

摘要（187）

PDF（pc）（1573KB）（358）

Three different zeolite catalysts with different pore sizes (MFI-type, BEA-type, and FAU-type zeolites) have been prepared. The influence of different zeolite catalysts on reactivity and product shape selectivity of tetralin is investigated. Clear differences are observed in the reactivity of tetralin and distribution of products produced by different catalysts. The diffusion and adsorption of the reactant tetralin and its intermediates, n-butylbenzene and 1-methyl indan, under the reaction conditions are calculated using molecular simulation methods. Combining simulation results and experimental observations, it is shown that the difference in diffusion coefficient and competitive adsorption capacity can explain the reactivity of tetralin and the selectivity of products. The steric hindrance of MFI-type zeolite mainly limits the key step of ring opening of tetralin, leading lower selectivity of ring-open products. N-butylbenzene molecules diffuse sufficiently fast in the large pores of FAU-type zeolite and the weak adsorption capacity of n-butylbenzene leads to its insufficient cracking. In addition, it also explains the reason that BEA-type zeolite has the best BTX selectivity, because it can satisfy both good ring-opening activity and sufficient butylbenzene cracking depth. Key words: hydrocracking; tetralin; molecular simulation; diffusion; competitive adsorption.

参考文献 | 相关文章 | 多维度评价

Select

12. 硼酸、磷酸对改善复合钙基润滑脂硬化现象的机理探讨

郑会孙洪伟何懿峰苏朔庄敏阳刘欣阳

2019, 21 (4): 112-118.

摘要（180）

PDF（pc）（483KB）（706）

In the 1950’s, complex calcium lubricating grease had been widely used. However, due to the hardening problem in the process of storage and use, the production of complex calcium lubricating grease decreases year by year. Domestic and foreign researchers have done a lot of work on its hardening problem, and it has been found that boric acid and phosphoric acid can effectively improve the hardening problem. In this paper, the water absorption test of several calcium salts was carried out, and it was found that calcium 12-hydroxystearate did not absorb water, and calcium acetate, calcium phosphate and calcium borate had different degrees of water absorption. Calcium acetate has the highest water absorption rate, and calcium phosphate and calcium borate have comparable water absorption rates. Using molecular simulation technology, it is found that in the complex calcium grease system, calcium phosphate and calcium borate prefers to combine with water, which inhibits the water absorption of calcium acetate and makes the hardening problem better.

相关文章 | 多维度评价

Select

13. Research on the impact of the new and renewable energy replacing fossil energy resources under constraint of carbon emissions

赵立祥杨楚潇

2019, 21 (4): 58-67.

摘要（178）

PDF（pc）（653KB）（1325）

For studying new and renewable energy substitutes fossil energy in primary energy consumption and its impact on carbon emissions in confront with economic uncertainties, a multi-sector DSGE model was employed to simulate the dynamic impact on carbon emissions and macroeconomy development. The structural adjustment of energy consumption and the carbon emissions mitigation policy were considered in the model. The simulation results showed that using new and renewable energy instead of fossil energy is the optimal choice for the firms under the constraint of carbon emission mitigation policy. Structure adjustment of energy consumption is the best routine to achieve the dual goal of economic development and carbon emission reduction goal. Unexpected sharp fall in free carbon quota has a negative impact on the economy.

参考文献 | 相关文章 | 多维度评价

Select

14. 炼化一体化项目多个相互连接蒸汽动力系统设计优化

白浩博李士雨王徐鹏刘昶

2020, 22 (4): 126-136.

摘要（175）

PDF（pc）（1898KB）（450）

在炼化一体化项目中，有一个动力中心(CUS , centralized utility system)用来集成各生产装置蒸汽需求，还有两个分别位于炼厂和乙烯厂中的子蒸汽动力系统(SUSs, sub-utility systems)为工艺过程提供驱动力。SUSs的结构和操作条件会影响炼油和乙烯装置的蒸汽需求，因此很难确定CUS的蒸汽产量。为了探究CUS和SUSs间复杂的相互影响，本文提出了一个混合整数非线性规划模型(MINLP, mixed-integer nonlinear programming)，以实现多个相互连接蒸汽动力系统设计优化，从而降低系统年度总费用(TAC, total annualized cost)。本文还建立了一个包含CUS和SUSs厂间蒸汽连接管道的超结构，同时提出了一个更准确的复杂蒸汽透平模型。将本文建立的MINLP模型用于某新建炼化一体化项目。为探究蒸汽主管温度对系统结构和操作条件的影响，研究了两个不同场景下的案例。通过优化主管温度，使系统TAC降低了$2,700,000。从优化结果可知，本文建立的优化模型可以有效解决多个相互连接蒸汽动力系统设计优化问题。

参考文献 | 相关文章 | 多维度评价

Select

15. 渣油加氢创新失活模型的应用

张奎聂红戴立顺

中国炼油与石油化工 2021, 23 (2): 11-20.

摘要（174）

PDF（pc）（2154KB）（254）

This article reports a new catalyst deactivation model for residue hydrotreating technology (RHT) with three adjustable parameters, named as "active-region-migration model". Active-region-migration model is proposed to describe the catalyst deactivation of RHT where the catalysts are deactivated due to metal loading. Along with the lumped reaction kinetics, the deactivation model can be applied to simulate the hydrogenation reaction performance in RHT. Industrial data from a commercial RHT unit show reasonably good agreements with the model calculations. Essentially, active-region-migration model can separately simulate the catalytic-activity change of each hydrogenation reaction during the whole run of RHT, with a single curve.

相关文章 | 多维度评价

Select

16. UASB反应器内厌氧氨氧化与硫自养反硝化耦合实现完全脱氮研究

国亚东白雪于海彤李雪晨赵朝成刘春爽

2020, 22 (1): 111-117.

摘要（173）

PDF（pc）（671KB）（603）

在UASB反应器内通过厌氧氨氧化与自养反硝化耦合作用实现完全脱氮。当总氮去除率从0.46 kgN/(m3 d) 逐渐增加到0.96 kgN/(m3 d)时，出水总氮浓度均低于3.0mg-N/L. 该耦合工艺对进水亚硝酸盐与氨氮比例不敏感，当亚硝酸盐与氨氮比例在1.35-1.55变化时能够实现完全脱氮。体系内单质硫的投加量能够调节自养反硝化菌与厌氧氨氧化菌之间的竞争。高通量测序表明Candidatus_Kuenenia和Thiobacillus是反应器内功能性厌氧氨氧化菌和自养反硝化菌。本研究为厌氧氨氧化技术规模化应用提供理论和技术基础。

相关文章 | 多维度评价

Select

17. 节能技术在三氯硅烷精馏提纯工艺中的应用

郄思远庞伟伟赵明黄哲庆

2019, 21 (3): 94-102.

摘要（172）

PDF（pc）（470KB）（678）

The trichlorosilane (TCS) purification process consumes a significant amount of energy to achieve the high purity requirement for TCS quality (99.9999%). This work proposed a series of energy saving technology to enhance the TCS purification process, including the conventional process, the conventional process coupled with heat-pump (HP), the multi-effect distillation process, and the dividing-wall columns process. All proposed schemes have been conceptually constructed by Aspen Plus. The design and optimization of the processes have been performed by the sensitivity analysis and the response surface methodology. Moreover, the energy consumption and total annual cost (TAC) for these schemes were discussed. The simulation results show that the TAC of the conventional process coupled with the integrated heat pump can reduce 50.5% of energy consumption as compared with the conventional process; the double-effect and three-effect processes can save 15.6% and 33.8% of energy consumption, respectively; the dividing wall column process and that coupled with the heat pump process can reduce by 22.3% and 48.1% of energy consumption, respectively. It can be found that the operating cost can be saved by using the heat pump technology, while the capital cost increases due to the investment in the compressor, when the processes coupled with the heat pump are used. These results demonstrate that the conventional process coupled with the HP technology has advantages over other distillation schemes for TCS purification in terms of the energy saving and economic effects.

相关文章 | 多维度评价

Select

18. 我国典型中间基原油炼化一体化加工方案的技术经济分析与生命周期评价

周鑫闫昊冯翔赵辉刘熠斌陈小博杨朝合

2020, 22 (4): 35-45.

摘要（167）

PDF（pc）（1920KB）（525）

炼化一体化（IRPUs）已成为石化工业可持续发展的必然选择。选择这样的配置可以提高石油资源的利用效率。然而，将经济和环境影响纳入IRPUs模型仍然是一个巨大的挑战。本文在Aspen HYSYSTM平台上建立了TEA-GHG-OPWM（面向全厂的技术经济分析和温室气体排放模型）模型，计算了减压渣油加氢裂化（VRHCRU）和减压渣油脱硫（VRDS-RFCC）两种方案的能耗、技术经济性和温室气体排放。此外，还开发了一种新的加工途径VGOHDT-HTMP-DC（减压蜡油加氢处理-加氢与TMP耦合工艺-延迟焦化），以期在千万元产值的基础上寻求提高经济效益和减少温室气体排放的方法。结果表明，VRHCRU比VRDS-RFCC（817.03 tCO2 eq·TMYOV-1·h-1）和VGOHDT-HTMP-DC（721.96 t CO2 eq·TMYOV-1·h-1）具有更高的能耗和温室气体排放量（877.11 t CO2 eq·TMYOV-1·h-1）。VGOHDT-HTMP-DC工艺的原料消耗、氢气消耗、能耗和温室气体排放最低，表明VGOHDT-HTMP-DC具有良好的经济性和环保性。

相关文章 | 多维度评价

Select

19. 碳包覆镍纳米复合材料在锂硫电池正极中的应用

杨宇翔谢婧新吴耿煌朱娜李欢荣峻峰

中国炼油与石油化工 2021, 23 (4): 1-6.

摘要（165）

PDF（pc）（882KB）（179）

锂硫电池有望成为下一代高能量密度储能设备。近年来，“电催化”的概念被引入锂硫电池领域中，一些过渡金属被证明可以催化含硫物质的电化学转化反应。本工作中，比表面积为146 m2/g的碳包覆镍纳米材料对于硫正极的电化学反应具有电催化作用。加入碳包覆镍材料后，Ni@C/G-S电池获得了比G-S电池更好的电化学性能。在此基础上，通过对碳包覆镍的碳壳表面进行化学改性，进一步提高了锂硫电池的可逆比容量和循环稳定性。此外，本文详细研究了碳壳不同元素掺杂对锂硫电池性能的影响。N-Ni@C-G/S电池在0.2 C、0.5 C和1.0 C倍率下实现了更高的比容量，分别为1229 mAh/g、927 mAh/g和830 mAh/g；而B-Ni@C-G/S电池具有最好的循环稳定性。

相关文章 | 多维度评价

Select

20. 离子液体催化碳酸乙烯酯和甲醇酯交换反应及其理论过程模拟

郭立颖吴浩王亦荣

2019, 21 (4): 73-80.

摘要（164）

PDF（pc）（865KB）（625）

首先合成了三种离子液体[Bmim]OH、[Bmim]IM和[Bmim]PF6，并对其化学结构进行了红外表征。再将其分别与助催化剂CaO、K2CO3和(CH3O)2Mg复合，研究离子液体复合体系催化碳酸乙烯酯和甲醇合成碳酸二甲酯的反应过程。通过正交试验研究了不同离子液体、助催化剂和反应温度对催化剂性能的影响。利用密度泛函理论研究了离子液体中阳离子和阴离子以及助催化剂的路易斯碱位对催化活性的协同关系，证明了一种易于制备的功能化咪唑盐具有较高的催化活性。碳酸乙烯酯的单程转化率为65.23%，碳酸二甲酯二甲基选择性为98.95%。通过实验和DFT研究，提出了反应机理。

参考文献 | 相关文章 | 多维度评价

摘要点击排行