Based on a typical gas composition from a methanol-to-propylene (MTP) reactor, and guided by a requirement to recover both propylene and ethylene, three separation strategies are studied and simulated by using PROI1 p...Based on a typical gas composition from a methanol-to-propylene (MTP) reactor, and guided by a requirement to recover both propylene and ethylene, three separation strategies are studied and simulated by using PROI1 package. These strategies are sequential separation, front-end dethanization, and front-end depropanization. The process does not involve an ethylene refrigeration system, using the separated stream as absorbent, and absorbing further the medium-pressure demethanization, and a proprietary technology by combining intercooling oil absorption and throttle expansio n. In fluences of different process streams as absorbent are studied on energy consumptions, propylene and ethylene recovery percentages, and other key-performance indicators of the separation strategies. Based on a commercial MTP plant with a methanol capacity of 1700 kt·a^-1, the simulated results show that the front-end dethanization using the C4 mixture as absorbent is the optimal separation strategy, in which the standard fuel oil consumption (a key-performance in dicator of energy con sumption) is 18.97 kt·h^-1, the total power consumption of two compressors is 22.4 MW, the propylene recovery percentage is 99.70%, and the ethylene recovery percentage is 99.70%. For a further improvement, the pre-dethanization and thermal coupling methods are applied. By using front-end pre-dethanization (partial cutting) with debutanizeroverhead, i.e. the C4 mixture, as absorbent, the power consumption of the compressors decreases to 19.9 MW, an 11% reduction compared with the clear-cutting method. The energy consumption for the dual compressors for crude gaseous product mixture and main product propylene refrigeration is 16.69 MW, 16.55% lower than that of the present MTP industrial plant with the same scale, and a total energy consumption of 20 MW for the triple compressors including product gas mixture compression, and ethylene and propylene refrigeration.展开更多
In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and wer...In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and were correlated by using Peng-Robinson model. The average relative error ofpropylene concentration in liquid phase is 1. 46 %. The results indicate that the models are very suitablefor the ternary system and the data are reliable.展开更多
One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on t...One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene （MTP） over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity （45.9%） was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.展开更多
Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a tempe...Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a temperature of 480 ℃; a methanol WHSV of 3 h-1; a methanol partial pressure of 30 k Pa; and a time on stream of 12 h, 24 h and 48 h, respectively. The BET parameters of catalysts and diffusion coefficients of toluene showed that there were two types of mesopores generated under different hydrothermal conditions. Mild temperature and moderate CAWF conditions led to external open mesopores which could be entered from the external surface of the zeolite, while a high temperature or a high CAWF condition resulted in the generation of macropores or internal isolated mesopores, which were occluded in the microporous matrix. The TGA results showed that catalyst with external open mesopores had good ability to resist coke accumulation and good performance on propylene selectivity, while the internal isolated mesopores did no contribute to the increased diffusivity of reactants and products.展开更多
调整双季铵盐表面活性剂与单季铵盐表面活性剂的使用量,通过协同晶化的方式合成了高结晶度、高介孔容的薄层ZSM-5沸石。利用XRD、XRF、SEM、TEM、NH3-TPD、低温氮气物理吸脱附以及27Al MAS NMR对沸石样品进行表征,并评价其甲醇制丙烯反...调整双季铵盐表面活性剂与单季铵盐表面活性剂的使用量,通过协同晶化的方式合成了高结晶度、高介孔容的薄层ZSM-5沸石。利用XRD、XRF、SEM、TEM、NH3-TPD、低温氮气物理吸脱附以及27Al MAS NMR对沸石样品进行表征,并评价其甲醇制丙烯反应(MTP)催化性能。结果表明,薄层沸石的b轴厚度随着双季铵盐表面活性剂使用量的减少而增加,适量的单季铵盐表面活性剂的加入可以起到协同晶化的作用,能够有效稳定胶束,从而调控沸石的形貌。优化2种季铵盐表面活性剂的使用量所得薄层ZSM-5沸石的比表面积和介孔孔容都有所增加,在甲醇制丙烯反应中的活性稳定性也得到较大改善。此外,协同晶化的方式减少了双季铵盐表面活性剂的使用,有利于降低薄层ZSM-5沸石的合成成本。展开更多
At present, methanol to propylene(MTP) technology developed by Lurgi Company is adopted for commercial plants and refined methanol with the purity ≥99.85 wt% is required as the feed of MTP unit in Lurgi's technol...At present, methanol to propylene(MTP) technology developed by Lurgi Company is adopted for commercial plants and refined methanol with the purity ≥99.85 wt% is required as the feed of MTP unit in Lurgi's technology.Therefore, high energy cost for refined methanol production is one of the bottlenecks to improve the economy of MTP technology. Reducing the grade of feed refined methanol may be an effective method to save energy and reduce operation costs in MTP process. In this work, experiments and process simulation were carried out to investigate the influence and feasibility of degrading the methanol feed. Experiments were conducted to investigate the influence of crude methanol feed on conversion and selectivity of MTP reaction as well as the performance of ZSM-5 catalyst. The experimental results showed that degrading the methanol feed had no obvious influence on the conversion and selectivity of MTP reactions and the catalyst deactivation was caused by the carbon accumulation and metals deposition on the active sites. The process simulation results showed that the influence on the conversion and selectivity as well as the stream load of MTP process was negligible if 98 mol% methanol was used as feed. Finally, industrial experiments were conducted by adjusting the operation parameters to degrade of feed methanol of the commercial 500 kt·a^(-1) MTP unit of Ningmei Group in China. The results of industrial application illustrated that annually 180 kt fuel coal and 150 kt desalted water as well as 1770 MW·h^(-1) electricity would be saved when the water content increased from 0.01% to 0.4%. This work has identified the feasibility to improve MTP technology by degrading the methanol feed.展开更多
The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benig...The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benign way.The catalysts commonly used for MTO process faces several challenges such as poor selectivity control,low hydrothermal stability and short lifetime.In the present study,we prepared a series of mordenite zeolites with variable Al contents(Si/Al molar ratios of 51−436)by a sequential dealumination treatment of air‐calcination and acid leaching.The textural properties,acidity and Al location before and after the dealumination treatment have been systematically studied and their effect on MTO especially the methanol to propylene(MTP)performance was thoroughly investigated.The mordenite zeolites with the Si/Al ratios over 150 selectively catalyzed methanol conversion in the MTP pathway,providing a high propylene selectivity of 63%and propylene/ethylene ratio of>10.Compared to the low‐silica MOR catalysts,highly dealuminated MOR showed much higher stability and longer lifetime,which can be further enhanced via harsh hydrothermal pretreatment.Furthermore,the lifetime was highly related to the crystal size along c‐axis.The excellent performance of highly dealuminated MOR is likely ascribed to the mesopores formed upon dealumination and the scarce Al sites located in the T sites shared by the 8‐member ring(MR)side pockets and 12‐MR pore channels.展开更多
This paper describes the hydrogenation of impurities in the methanol-containing effluent from the propylene epoxidation process with hydrogen peroxide. The effects of reaction temperature, pressure, weight hourly spac...This paper describes the hydrogenation of impurities in the methanol-containing effluent from the propylene epoxidation process with hydrogen peroxide. The effects of reaction temperature, pressure, weight hourly space velocity(WHSV) and H2/methanol ratio on the concentration of various impurities in methanol solvent were investigated. It was found out that the aldehyde, hydrogen peroxide and nitro compounds in the methanol solvent could be completely hydrogenated over the Ni catalyst under proper reaction conditions. 90% of acetone and up to 50% of acetals(ketals) existing in the methanol solvent could be hydrogenated. No significant change was observed for the rest of the impurities that were present in the methanol solvent(i. e., 1-methoxy-2-propanol, 2-methoxy-1-propanol and 1,2-propanediol). The H2O2 decomposition reaction was enhanced using Ni catalyst, through the formation of NioOH, but no oxygen was found in the off-gas of hydrogenation reaction since NioH could react on NioOH formed via dissociative adsorption of hydrogen peroxide, or on NioO formed via adsorption of oxygen.展开更多
Methanol to olefins(MTO)reaction as an important non-oil route to produce light olefins has been industrialized,and received over 80% ethylene plus propylene selectivity.However,to achieve high single ethylene or prop...Methanol to olefins(MTO)reaction as an important non-oil route to produce light olefins has been industrialized,and received over 80% ethylene plus propylene selectivity.However,to achieve high single ethylene or propylene selectivity towards the fluctuated market demand is still full of challenge.Small-pore SAPO-14 molecular sieve is a rare MTO catalyst exhibiting extra-high propylene selectivity.It provides us a valuable clue for further understanding of the relationship between molecular sieve structure and MTO catalytic performance.In this work,a seconds-level sampling fixed-bed reactor was used to capture real-time product distributions,which help to achieve more selectivity data in response to very short catalytic life of SAPO-14.Changes in product distribution,especially during the low activity stage,reflect valuable information on the reaction pathway.Combined with in situ diffuse reflectance infrared Fourier-transform spectroscopy,in situ ultraviolet Raman measurements and ^(12)C/^(13)C isotopic switch experiments,a reaction pathway evolution from dual cycle to olefins-based cycle dominant was revealed.In addition,the deactivation behaviors of SAPO-14 were also investigated,which revealed that polymethylbenzenes have been the deactivated species in such a situation.This work provides helpful hints on the development of characteristic methanol to propylene(MTP)catalysts.展开更多
On September 14,2015 the 10 kt/a-class commercialized test project relating to the technology for methanolto-butene production with co-production of propylene(hereafter abbreviated as CMTX)has passed the scientific ac...On September 14,2015 the 10 kt/a-class commercialized test project relating to the technology for methanolto-butene production with co-production of propylene(hereafter abbreviated as CMTX)has passed the scientific achievement appraisal organized by the China Petroleum and Chemical Industries Federation(CPCIF).展开更多
A novel copolymer of polyaniline-poly(propylene oxide) (PAN-PPO) was prepared by cyclic voltammetry (CV) and characterized by FTIR and SEM. It showed good electroactivity for methanol oxidation in H2SO4 solution.
基金Supported by Sinopec Group company commissioned development project(contract number:412101)
文摘Based on a typical gas composition from a methanol-to-propylene (MTP) reactor, and guided by a requirement to recover both propylene and ethylene, three separation strategies are studied and simulated by using PROI1 package. These strategies are sequential separation, front-end dethanization, and front-end depropanization. The process does not involve an ethylene refrigeration system, using the separated stream as absorbent, and absorbing further the medium-pressure demethanization, and a proprietary technology by combining intercooling oil absorption and throttle expansio n. In fluences of different process streams as absorbent are studied on energy consumptions, propylene and ethylene recovery percentages, and other key-performance indicators of the separation strategies. Based on a commercial MTP plant with a methanol capacity of 1700 kt·a^-1, the simulated results show that the front-end dethanization using the C4 mixture as absorbent is the optimal separation strategy, in which the standard fuel oil consumption (a key-performance in dicator of energy con sumption) is 18.97 kt·h^-1, the total power consumption of two compressors is 22.4 MW, the propylene recovery percentage is 99.70%, and the ethylene recovery percentage is 99.70%. For a further improvement, the pre-dethanization and thermal coupling methods are applied. By using front-end pre-dethanization (partial cutting) with debutanizeroverhead, i.e. the C4 mixture, as absorbent, the power consumption of the compressors decreases to 19.9 MW, an 11% reduction compared with the clear-cutting method. The energy consumption for the dual compressors for crude gaseous product mixture and main product propylene refrigeration is 16.69 MW, 16.55% lower than that of the present MTP industrial plant with the same scale, and a total energy consumption of 20 MW for the triple compressors including product gas mixture compression, and ethylene and propylene refrigeration.
文摘In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and were correlated by using Peng-Robinson model. The average relative error ofpropylene concentration in liquid phase is 1. 46 %. The results indicate that the models are very suitablefor the ternary system and the data are reliable.
文摘One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene （MTP） over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity （45.9%） was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.
基金supported by the National Natural Science Foundation of China(Grant 21176208&61590925)the National High-Tech R&D Program of China(Grant 2012AA030304)+1 种基金the International S&T Cooperation Projects of China(2015DFA40660)the Fundamental Research Funds for the Central Universities(Grant2015QNA4033)
文摘Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a temperature of 480 ℃; a methanol WHSV of 3 h-1; a methanol partial pressure of 30 k Pa; and a time on stream of 12 h, 24 h and 48 h, respectively. The BET parameters of catalysts and diffusion coefficients of toluene showed that there were two types of mesopores generated under different hydrothermal conditions. Mild temperature and moderate CAWF conditions led to external open mesopores which could be entered from the external surface of the zeolite, while a high temperature or a high CAWF condition resulted in the generation of macropores or internal isolated mesopores, which were occluded in the microporous matrix. The TGA results showed that catalyst with external open mesopores had good ability to resist coke accumulation and good performance on propylene selectivity, while the internal isolated mesopores did no contribute to the increased diffusivity of reactants and products.
文摘调整双季铵盐表面活性剂与单季铵盐表面活性剂的使用量,通过协同晶化的方式合成了高结晶度、高介孔容的薄层ZSM-5沸石。利用XRD、XRF、SEM、TEM、NH3-TPD、低温氮气物理吸脱附以及27Al MAS NMR对沸石样品进行表征,并评价其甲醇制丙烯反应(MTP)催化性能。结果表明,薄层沸石的b轴厚度随着双季铵盐表面活性剂使用量的减少而增加,适量的单季铵盐表面活性剂的加入可以起到协同晶化的作用,能够有效稳定胶束,从而调控沸石的形貌。优化2种季铵盐表面活性剂的使用量所得薄层ZSM-5沸石的比表面积和介孔孔容都有所增加,在甲醇制丙烯反应中的活性稳定性也得到较大改善。此外,协同晶化的方式减少了双季铵盐表面活性剂的使用,有利于降低薄层ZSM-5沸石的合成成本。
基金Supported by the National Key R&D Program of China(2017YFB0601902)
文摘At present, methanol to propylene(MTP) technology developed by Lurgi Company is adopted for commercial plants and refined methanol with the purity ≥99.85 wt% is required as the feed of MTP unit in Lurgi's technology.Therefore, high energy cost for refined methanol production is one of the bottlenecks to improve the economy of MTP technology. Reducing the grade of feed refined methanol may be an effective method to save energy and reduce operation costs in MTP process. In this work, experiments and process simulation were carried out to investigate the influence and feasibility of degrading the methanol feed. Experiments were conducted to investigate the influence of crude methanol feed on conversion and selectivity of MTP reaction as well as the performance of ZSM-5 catalyst. The experimental results showed that degrading the methanol feed had no obvious influence on the conversion and selectivity of MTP reactions and the catalyst deactivation was caused by the carbon accumulation and metals deposition on the active sites. The process simulation results showed that the influence on the conversion and selectivity as well as the stream load of MTP process was negligible if 98 mol% methanol was used as feed. Finally, industrial experiments were conducted by adjusting the operation parameters to degrade of feed methanol of the commercial 500 kt·a^(-1) MTP unit of Ningmei Group in China. The results of industrial application illustrated that annually 180 kt fuel coal and 150 kt desalted water as well as 1770 MW·h^(-1) electricity would be saved when the water content increased from 0.01% to 0.4%. This work has identified the feasibility to improve MTP technology by degrading the methanol feed.
文摘The growing consumption of light olefins has stimulated intensive researches on methanol to olefin(MTO)process which possesses great advantages for coal conversion to value‐added chemicals in an environmentally benign way.The catalysts commonly used for MTO process faces several challenges such as poor selectivity control,low hydrothermal stability and short lifetime.In the present study,we prepared a series of mordenite zeolites with variable Al contents(Si/Al molar ratios of 51−436)by a sequential dealumination treatment of air‐calcination and acid leaching.The textural properties,acidity and Al location before and after the dealumination treatment have been systematically studied and their effect on MTO especially the methanol to propylene(MTP)performance was thoroughly investigated.The mordenite zeolites with the Si/Al ratios over 150 selectively catalyzed methanol conversion in the MTP pathway,providing a high propylene selectivity of 63%and propylene/ethylene ratio of>10.Compared to the low‐silica MOR catalysts,highly dealuminated MOR showed much higher stability and longer lifetime,which can be further enhanced via harsh hydrothermal pretreatment.Furthermore,the lifetime was highly related to the crystal size along c‐axis.The excellent performance of highly dealuminated MOR is likely ascribed to the mesopores formed upon dealumination and the scarce Al sites located in the T sites shared by the 8‐member ring(MR)side pockets and 12‐MR pore channels.
文摘This paper describes the hydrogenation of impurities in the methanol-containing effluent from the propylene epoxidation process with hydrogen peroxide. The effects of reaction temperature, pressure, weight hourly space velocity(WHSV) and H2/methanol ratio on the concentration of various impurities in methanol solvent were investigated. It was found out that the aldehyde, hydrogen peroxide and nitro compounds in the methanol solvent could be completely hydrogenated over the Ni catalyst under proper reaction conditions. 90% of acetone and up to 50% of acetals(ketals) existing in the methanol solvent could be hydrogenated. No significant change was observed for the rest of the impurities that were present in the methanol solvent(i. e., 1-methoxy-2-propanol, 2-methoxy-1-propanol and 1,2-propanediol). The H2O2 decomposition reaction was enhanced using Ni catalyst, through the formation of NioOH, but no oxygen was found in the off-gas of hydrogenation reaction since NioH could react on NioOH formed via dissociative adsorption of hydrogen peroxide, or on NioO formed via adsorption of oxygen.
文摘Methanol to olefins(MTO)reaction as an important non-oil route to produce light olefins has been industrialized,and received over 80% ethylene plus propylene selectivity.However,to achieve high single ethylene or propylene selectivity towards the fluctuated market demand is still full of challenge.Small-pore SAPO-14 molecular sieve is a rare MTO catalyst exhibiting extra-high propylene selectivity.It provides us a valuable clue for further understanding of the relationship between molecular sieve structure and MTO catalytic performance.In this work,a seconds-level sampling fixed-bed reactor was used to capture real-time product distributions,which help to achieve more selectivity data in response to very short catalytic life of SAPO-14.Changes in product distribution,especially during the low activity stage,reflect valuable information on the reaction pathway.Combined with in situ diffuse reflectance infrared Fourier-transform spectroscopy,in situ ultraviolet Raman measurements and ^(12)C/^(13)C isotopic switch experiments,a reaction pathway evolution from dual cycle to olefins-based cycle dominant was revealed.In addition,the deactivation behaviors of SAPO-14 were also investigated,which revealed that polymethylbenzenes have been the deactivated species in such a situation.This work provides helpful hints on the development of characteristic methanol to propylene(MTP)catalysts.
文摘On September 14,2015 the 10 kt/a-class commercialized test project relating to the technology for methanolto-butene production with co-production of propylene(hereafter abbreviated as CMTX)has passed the scientific achievement appraisal organized by the China Petroleum and Chemical Industries Federation(CPCIF).
文摘A novel copolymer of polyaniline-poly(propylene oxide) (PAN-PPO) was prepared by cyclic voltammetry (CV) and characterized by FTIR and SEM. It showed good electroactivity for methanol oxidation in H2SO4 solution.
