Nitrous oxide(N_(2)O),as an important gas affecting climate warming,is attracting attention from allwalks of life.This reviewaddresses N_(2)O emissions status in the adipic acid industry,a significant industrial green...Nitrous oxide(N_(2)O),as an important gas affecting climate warming,is attracting attention from allwalks of life.This reviewaddresses N_(2)O emissions status in the adipic acid industry,a significant industrial greenhouse gas source.It elucidates the N_(2)O emission mechanism and influencing factors in adipic acid production.It extensively evaluates N_(2)O emission accounting methods,including Intergovernmental Panel on Climate Change(IPCC)Guidelines,World Resources Institute(WRI)Protocol,and others.While the IPCC emission factor method offers simplicity and comparability,it may lack precision for facilities with advanced emission reduction measures.To address this,a combined modeling and monitoring approach is advocated.It scrutinizes modeling methods(statistical techniques,Greenhouse Gas and Air Pollution Interactions and Synergies,and Life-cycle Assessment)and highlights their reliance on specific data and perspectives.It emphasizes the growing importance of on-site monitoring with mid-IR technology.Additionally,it underscores the potential of aircraft-based and satellite remote sensing for comprehensive N_(2)O emissions data.The reviewalso highlights recent advancements in emission mitigation,particularly in adipic acid synthesis techniques,showing substantial potential for N_(2)O reduction.Innovative paradigms and strategies for N_(2)O mitigation in the adipic acid industry are presented,with a focus on achieving nitrogen oxides(NO_(x))-free production.These approaches hold promise for emission reduction,given the high removal efficiency in plant end-of-treatment processes.Various accounting methods,monitoring techniques,and mitigation strategies were integrated and analyzed to provides a comprehensive overview of N_(2)O emissions in the adipic acid industry,with the aim of guiding future research and policy initiatives.展开更多
In this manuscript,we conveniently prepared a series of polyester-polycarbonate copolymer(PPC-P)/polybutylene adipate terephthalate(PBAT)blends that exhibit both flame-retardant properties and toughness.Piperazine pyr...In this manuscript,we conveniently prepared a series of polyester-polycarbonate copolymer(PPC-P)/polybutylene adipate terephthalate(PBAT)blends that exhibit both flame-retardant properties and toughness.Piperazine pyrophosphate(PAPP),melamine phosphate(MPP)and ZnO were used as synergistic flame retardants for PPC-P/PBAT blends.The effects of synergistic flame retardants on thermal stability,combustion behavior and flame retardancy of PPC-P/PBAT blends were investigated.The results showed that when the ratio of PAPP/MPP/ZnO was 18.4:9.2:2.4,the LOI of PPC-P/PBAT composite was 42.8%,and UL-94 reached V-0 level.The results of cone calorimetry showed that the mass loss rate(MLR),the peak value of the biggest smoke production rate(pSPR)and total smoke production(TSP)of the material decreased,and a continuously expanded carbon layer with a compact structure was formed after combustion.The carbon layer formed after surface combustion protects the material from decomposition over a long temperature range.In terms of mechanical properties,compared with the composites with only PAPP and MPP,PAPP/MPP/ZnO composites can improve the mechanical properties.After adding 2.4 wt% ZnO,the tensile strength and impact strength of the polymer increased to 34.2 MPa and 28.5 kJ/m^(2),respectively.The results showed that the use of non-toxic,environmentally friendly,halogen-free flame retardants to enhance the flame retardant properties of biodegradable polymer composites is a promising direction in the future.展开更多
The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synth...The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synthesis method,in which titanium and manganese coexist within the zeolite matrix,as characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,ultraviolet,extended X-ray absorption fine structure etc.The introduction of matrix Mn species(Mn^(3+),Mn^(4+))not only increased the surface oxygen vacancies,but also generated medium-strong acid sites,which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination.On HMTS-3,one-pot oxidation of cyclohexane at 140℃and 2 MPa O_(2)gave 81.6%conversion and 71.5%AA selectivity,the highest value obtained at present.Control experiments with single-component samples confirmed that matrix Ti^(4+)catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol(KA oil),and matrix Mn favored the conversion of KA oil to AA.The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity.Specifically,the matrix Ti^(4+)might activate oxygen to form Ti-O_(2)2-which facilitated the activation of the C-H bond of cyclohexane.The activation of O_(2)on matrix Mn^(3+)formed Mn^(4+)-O_(2)-favoring the breaking of the C-C bond of cyclohexanone.The hierarchical structure not only exposed more active sites and promoted mass transfer,but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti,which facilitated the overall reaction.This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.展开更多
Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems.However,the development o...Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems.However,the development of highly-active bifunctional electrocatalysts remains a challenge.Herein,3D hierarchical nickel-copper alloying arrays with dendritic morphology are manufactured by a simple electrodeposition process,standing for the excellent bifunctional electrocatalyst towards the co-production of adipic acid and H_(2)from cyclohexanone and water.The membrane-free flow electrolyzer of Cu_(0.81)Ni_(0.19)/NF shows the superior electrooxidation performance of ketone-alcohol(KA)oil with high faradaic efficiencies of over 90%for adipic acid and H_(2),robust stability over 200 h as well as a high yield of 0.6 mmol h^(-1) for adipic acid at 100 mA cm^(-2).In-situ spectroscopy indicates the Cu_(0.81)Ni_(0.19)alloy contributes to forming more active NiOOH species to involve in the conversion of cyclohexanone to adipic acid,while the proposed reaction pathway undergoes the 2-hydroxycyclohexanone and 2,7-oxepanedione intermediates.Moreover,the theoretical calculations confirm that the optimal electronic interaction,boosted reaction kinetics as well as improved adsorption free energy of reaction intermediates,synergistically endows Cu_(0.81)Ni_(0.19)alloy with superior bifunctional performance.展开更多
The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy （SEM） a...The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy （SEM） and transmission electron microscopy （TEM）, respectively. The corrosion resistance was evaluated by electrochemical impedance spectroscopy （EIS）. The results showed that the adipic acid was absorbed at the electrolyte/anodic layer interface during anodizing. The corrosion rate of anodic film decreased and the film thickness increased. The film was uniform and compact especially at the film/substrate interface. After sealing procedure, anodic film formed with the addition of adipic acid exhibited improved dielectric property and corrosion resistance in aggressive environment.展开更多
Using a laser detecting system, solubility data were measured for adipic acid dissolved in six pure solvents, namely, cyclohexanone, cyclohexanol, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethy...Using a laser detecting system, solubility data were measured for adipic acid dissolved in six pure solvents, namely, cyclohexanone, cyclohexanol, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide at the temperature range from 293.15K to 353.15K. All these data were regressed by 2h, NRTL, Wilson, and the modified Wilson models. For the study of six, 2h, NRTL, and the modified Wilson models were found to provide an accurate mathematical representation of the experimental results, with overall average absolute relative deviations between measured and calculated values as 1.74%, 2.06%, and 3.06%, respectively. The results showed that the λh model is the most suitable for description of the solid-liquid equilibrium containing adipic acid.展开更多
Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization beha...Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization behavior, crystallization kinetics and spherulite morphology of PEA. Upon addition of PPZn, the crystallization temperature and crystallinity of PEA in the non-isothermal crystallization process increased significantly. Analysis of crystallization kinetics by Avrami equation suggests that the crystallization time shortened greatly and crystallization rate increased markedly after addition of PPZn. In the presence of PPZn, the spherulite size decreased and spherulite density increased significantly. It suggests that PPZn is an efficient nucleating agent for the crystallization of PEA. The accelerated crystallization in the presence of PPZn is mainly attributed to the epitaxial nucleation of PEA crystals on the surface of PPZn crystals, that is, a perfect lattice matching between PEA crystal and PPZn crystal occurs.展开更多
Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]he...Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]heptane,trans/cis-cyclohexane-1,2-diol,cyclohex-2-en-1-ol,cyclohex-2-en-1-one,and even adipic acid.These products are broadly and abundantly used intermediates in the chemical industry;therefore,controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry,thus becoming the aim of synthetic and catalytic chemists in the field.Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance.This short review summarizes the recent advances on this subject,and the contents are mainly classified based on the chosen oxidants.We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.展开更多
Using a simple and reliable apparatus, the solubilities of adipic acid in water, ethanol, chloroform, n-butanol and acetone are determined by the analytic method. The results are correlated with λh equation, Apelblat...Using a simple and reliable apparatus, the solubilities of adipic acid in water, ethanol, chloroform, n-butanol and acetone are determined by the analytic method. The results are correlated with λh equation, Apelblat equation, and UNIFAC equation. The solubilities calculated by these models are in good agreement with experi-mental data, so that the models can meet the requirements of engineering design.展开更多
The reaction mechanism of the liquid phase ammoniation of adipic acid to adiponitrile was studied experimentally in a semi-batch reactor. Macrokinetics of the main and side reactions were identified to minimize corros...The reaction mechanism of the liquid phase ammoniation of adipic acid to adiponitrile was studied experimentally in a semi-batch reactor. Macrokinetics of the main and side reactions were identified to minimize corrosion and coking to prolong the operation period, to increase the yield of adiponitrile and to improve the design of the reactor. Macrokinetic equations of ammoniation-neutralization of adipic acid and dehydration were of first-order to adipic concentration cB≥3.5% and of second order for cB≥3.5%. Catalyst H3PO4 reduced the activation energy of neutralization and dehydration reactions of adipic acid and was significantly important for the second step of dehydration to produce adiponitrile.展开更多
Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses sign...Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses significant carbon footprint to the environment.Clean adipic acid synthesis methods using a heterogeneous catalyst with H2O2 as oxidant and water as solvent have potential advantages of low catalyst cost,easy synthesis and recovery,cleanness and environmental protection.In this work,hexagonal mesoporous silicate materials were synthesized by a sol–gel method and evaluated for cyclohexanol/cyclohexanone oxidation to adipic acid.The physical and chemical properties of Fe-HMS were characterized by XRD,HR-TEM,BET and UV–Vis.The experimental results showed that Fe-HMS materials show pore sizes ranging from 2–3 nm.W-and Mo-based polyoxometalates were also evaluated and compared to the Fe-based HMS catalysts.To improve the adipic acid yield,the influence of the transition metal as well as the effect of metal loading,reaction temperature and catalyst amount on the catalytic performances of Fe-HMS have been investigated in details.When Si/Fe atomic ratio=100,Fe-HMS catalyst shows the highest activity,with a cyclohexanone conversion of 92.3%and adipic acid selectivity of 29.4%.The reaction pathway of cyclohexanone oxidation was further proposed based on experimental data.展开更多
The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends we...The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends were studied by means of differential scanning calorimetry （DSC）, wide-angle X-ray diffraction （XRD） and atomic force microscopy （AFM）. It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors fiat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.展开更多
The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differen...The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edge- on lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the （00l） PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00l} lattice planes.展开更多
The adipic acid is an important intermediate in the production of nylon,polyurethane and polye ster resin s.The industrial approach for preparing adipic acid is through the liquid catalytic oxidation of KA oil with ni...The adipic acid is an important intermediate in the production of nylon,polyurethane and polye ster resin s.The industrial approach for preparing adipic acid is through the liquid catalytic oxidation of KA oil with nitric acid.In this work,a comprehensive model is developed for this reaction based on the kinetic study conducted in a continuous flow tubular reactor.The kinetic model fits well with the experimental results across the experimental conditions,and the average relative error between the calculated and experimental values is 5.7%.Results show that there was an induction period at the early stage of reaction.Moreover,it is found that at temperature range of 328-358 K,the formation rate of adipic acid strongly dependents on the temperature and nitric acid concentration.The developed model is used to predict the yield of adipic acid at 359-368 K.The work in this study could provide much knowledge for industrial tubular reactor design.展开更多
Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the con- tinuous esterification process of polyester polyols was developed, which was carried out in an innovational bub- bling ...Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the con- tinuous esterification process of polyester polyols was developed, which was carried out in an innovational bub- bling reactive distillation tower （BRDT） at atmospheric pressure. In this new type of reactor, direct esterification between ethylene glycol and adipic acid was accomplished efficiently and rapidly. A bench BRDT with the height of 2 m was applied for the esteriflcation process of l^oly （ethylene adlpate） （P＇EA）. In the continuous operation, Hn- ear oligomers were discharged from the bottom of the column, while water passed a few column trays and a pack- ing section as a condensation byproduct. The influence of major operating conditions on reactor performance was also simulated. Simulation results were in good agreement with experimental data, providing a strategy for devel- oping and optimizing this process.展开更多
Oriented and non-oriented Teflon films, which were found to have the same crystalline structure, but different surface morphologies, were used to sandwich poly（butylene adipate） （PBA） films during isothermal cryst...Oriented and non-oriented Teflon films, which were found to have the same crystalline structure, but different surface morphologies, were used to sandwich poly（butylene adipate） （PBA） films during isothermal crystallization. It was found that both the Teflon surface structure and the PBA polymorphic structure are the determining factors to induce epitaxial crystallization. The oriented Teflon film was able to induce epitaxial crystallization of PBA α crystal, while the non-oriented Teflon did not induce any epitaxial crystallization of PBA. Epitaxial crystallization did not occurred for PBA β crystals between neither the oriented nor the non-oriented Teflon films. The enzymatic degradation rate of PBA films was not determined by the epitaxial crystallization, in fact it was still dependent on the polymorphic crystal structure of PBA. The morphological changes of PBA films after enzymatic degradation confirmed again that the epitaxial crystallization only occurred for the PBA film with α crystal structure which was produced by being sandwiched between oriented Teflon films, and it happened only on the surface of PBA films.展开更多
The miscibility, isothermal crystallization kinetics and morphology of the poly（vinylidene fluoride）（PVDF）/poly（ethylene adipate）（PEA） blends have been studied by differential scanning calorimetry（DSC）, opti...The miscibility, isothermal crystallization kinetics and morphology of the poly（vinylidene fluoride）（PVDF）/poly（ethylene adipate）（PEA） blends have been studied by differential scanning calorimetry（DSC）, optical microscopy（OM） and scanning electron microscopy（SEM）. A depression of the equilibrium melting point of PVDF was observed. From the melting point data of PVDF, a negative but quite small value of the interaction parameter ？PVDF-PEA is derived using the Flory-Huggins equation, implying that PVDF shows miscibility with PEA to some extent. Nonisothermal and isothermal crystallization kinetics suggest that the crystallization rate of PVDF decreases with increasing the amount of PEA, and a contrary trend was found when PEA crystallizes with the increase of the amount of PVDF. It was further disclosed that the blend ratio and crystallization temperature affect the texture of PVDF spherulites greatly, which determines the subsequent crystallization of PEA. At high temperatures, e.g. 150 ℃, the band spacing of PVDF spherulites increases with the addition of PEA content and the spherulitic structure becomes more open. In this case, spherulitic crystallization of PEA is not observed for all blend compositions. At low temperatures, e.g. 130 ℃, for the PEA-rich blends, the interpenetrated structures are eventually formed by the penetration of the spherulites of PEA growing within the pre-existing PVDF spherulites.展开更多
The effects of PEA on the ）γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy （OM）, infrared spectroscopy ...The effects of PEA on the ）γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy （OM）, infrared spectroscopy （IR） and scanning electron microscopy （SEM）. The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within theγ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.展开更多
Adipic acid is an important petrochemical product,and its production process emits a high concentration of greenhouse gas N_2 O.This paper aims to provide quantitative references for relevant authorities to formulate ...Adipic acid is an important petrochemical product,and its production process emits a high concentration of greenhouse gas N_2 O.This paper aims to provide quantitative references for relevant authorities to formulate greenhouse gas control roadmaps.The forecasting method of this paper is consistent with the published national inventory in terms of caliber.Based on the N_2 O abatement technical parameters of adipic acid and the production trend,this paper combines the scenario analysis and provides a measurement of comprehensive N_2 O abatement effect of the entire industry in China.Four future scenarios are assumed.The baseline scenario(BAUS) is a frozen scenario.Three emission abatement scenarios(ANAS,SNAS,and ENAS) are assumed under different strength of abatement driving parameters.The results show that China's adipic acid production process can achieve increasingly significant N_2 O emission abatement effects.Compared to the baseline scenario,by 2030,the N_2 O emission abatements of the three emission abatement scenarios can reach 207-399 kt and the emission abatement ratios can reach 32.5%-62.6%.By 2050,the N_2 O emission abatements for the three emission abatement scenarios can reach 387-540 kt and the emission abatement ratios can reach 71.4%-99.6%.展开更多
基金supported by the National Key R&D Program of China(No.2023YFC3707201)the National Natural Science Foundation of China(No.52320105003)+1 种基金the Informatization Plan of Chinese Academy of Sciences(No.CAS-WX2023PY-0103)the Fundamental Research Funds for the Central Universities(No.E3ET1803).
文摘Nitrous oxide(N_(2)O),as an important gas affecting climate warming,is attracting attention from allwalks of life.This reviewaddresses N_(2)O emissions status in the adipic acid industry,a significant industrial greenhouse gas source.It elucidates the N_(2)O emission mechanism and influencing factors in adipic acid production.It extensively evaluates N_(2)O emission accounting methods,including Intergovernmental Panel on Climate Change(IPCC)Guidelines,World Resources Institute(WRI)Protocol,and others.While the IPCC emission factor method offers simplicity and comparability,it may lack precision for facilities with advanced emission reduction measures.To address this,a combined modeling and monitoring approach is advocated.It scrutinizes modeling methods(statistical techniques,Greenhouse Gas and Air Pollution Interactions and Synergies,and Life-cycle Assessment)and highlights their reliance on specific data and perspectives.It emphasizes the growing importance of on-site monitoring with mid-IR technology.Additionally,it underscores the potential of aircraft-based and satellite remote sensing for comprehensive N_(2)O emissions data.The reviewalso highlights recent advancements in emission mitigation,particularly in adipic acid synthesis techniques,showing substantial potential for N_(2)O reduction.Innovative paradigms and strategies for N_(2)O mitigation in the adipic acid industry are presented,with a focus on achieving nitrogen oxides(NO_(x))-free production.These approaches hold promise for emission reduction,given the high removal efficiency in plant end-of-treatment processes.Various accounting methods,monitoring techniques,and mitigation strategies were integrated and analyzed to provides a comprehensive overview of N_(2)O emissions in the adipic acid industry,with the aim of guiding future research and policy initiatives.
基金Financial support from National Natural Science Foundation of China(Grant No.22075298)National Key R&D Program of China(2022YFD2301204)is gratefully acknowledged.
文摘In this manuscript,we conveniently prepared a series of polyester-polycarbonate copolymer(PPC-P)/polybutylene adipate terephthalate(PBAT)blends that exhibit both flame-retardant properties and toughness.Piperazine pyrophosphate(PAPP),melamine phosphate(MPP)and ZnO were used as synergistic flame retardants for PPC-P/PBAT blends.The effects of synergistic flame retardants on thermal stability,combustion behavior and flame retardancy of PPC-P/PBAT blends were investigated.The results showed that when the ratio of PAPP/MPP/ZnO was 18.4:9.2:2.4,the LOI of PPC-P/PBAT composite was 42.8%,and UL-94 reached V-0 level.The results of cone calorimetry showed that the mass loss rate(MLR),the peak value of the biggest smoke production rate(pSPR)and total smoke production(TSP)of the material decreased,and a continuously expanded carbon layer with a compact structure was formed after combustion.The carbon layer formed after surface combustion protects the material from decomposition over a long temperature range.In terms of mechanical properties,compared with the composites with only PAPP and MPP,PAPP/MPP/ZnO composites can improve the mechanical properties.After adding 2.4 wt% ZnO,the tensile strength and impact strength of the polymer increased to 34.2 MPa and 28.5 kJ/m^(2),respectively.The results showed that the use of non-toxic,environmentally friendly,halogen-free flame retardants to enhance the flame retardant properties of biodegradable polymer composites is a promising direction in the future.
文摘The direct oxidation of cyclohexane to adipic acid(AA)without the use of HNO_(3)is important but still challenging.Herein,hierarchical manganese-containing TS-1 zeolite(HMTS)was prepared using an improved direct synthesis method,in which titanium and manganese coexist within the zeolite matrix,as characterized by X-ray diffraction,X-ray photoelectron spectroscopy,transmission electron microscopy,ultraviolet,extended X-ray absorption fine structure etc.The introduction of matrix Mn species(Mn^(3+),Mn^(4+))not only increased the surface oxygen vacancies,but also generated medium-strong acid sites,which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination.On HMTS-3,one-pot oxidation of cyclohexane at 140℃and 2 MPa O_(2)gave 81.6%conversion and 71.5%AA selectivity,the highest value obtained at present.Control experiments with single-component samples confirmed that matrix Ti^(4+)catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol(KA oil),and matrix Mn favored the conversion of KA oil to AA.The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity.Specifically,the matrix Ti^(4+)might activate oxygen to form Ti-O_(2)2-which facilitated the activation of the C-H bond of cyclohexane.The activation of O_(2)on matrix Mn^(3+)formed Mn^(4+)-O_(2)-favoring the breaking of the C-C bond of cyclohexanone.The hierarchical structure not only exposed more active sites and promoted mass transfer,but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti,which facilitated the overall reaction.This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.
基金financially supported by the National Natural Science Foundation of China(22205205,22472151)the Zhejiang Provincial Natural Science Foundation of China(LQ22B030008)the Science Foundation of Zhejiang Sci-Tech University(ZSTU)under Grant No.21062337-Y.
文摘Constructing electrocatalytic overall reaction technology to couple the electrosynthesis of adipic acid with energy-saving hydrogen production is of significant for sustainable energy systems.However,the development of highly-active bifunctional electrocatalysts remains a challenge.Herein,3D hierarchical nickel-copper alloying arrays with dendritic morphology are manufactured by a simple electrodeposition process,standing for the excellent bifunctional electrocatalyst towards the co-production of adipic acid and H_(2)from cyclohexanone and water.The membrane-free flow electrolyzer of Cu_(0.81)Ni_(0.19)/NF shows the superior electrooxidation performance of ketone-alcohol(KA)oil with high faradaic efficiencies of over 90%for adipic acid and H_(2),robust stability over 200 h as well as a high yield of 0.6 mmol h^(-1) for adipic acid at 100 mA cm^(-2).In-situ spectroscopy indicates the Cu_(0.81)Ni_(0.19)alloy contributes to forming more active NiOOH species to involve in the conversion of cyclohexanone to adipic acid,while the proposed reaction pathway undergoes the 2-hydroxycyclohexanone and 2,7-oxepanedione intermediates.Moreover,the theoretical calculations confirm that the optimal electronic interaction,boosted reaction kinetics as well as improved adsorption free energy of reaction intermediates,synergistically endows Cu_(0.81)Ni_(0.19)alloy with superior bifunctional performance.
基金Project(51271012)supported by the National Natural Science Foundation of China
文摘The influence of adipic acid on the formation and corrosion resistance of anodic oxide film fabricated on 2024 aluminum alloy was investigated. The morphology was investigated by scanning electron microscopy （SEM） and transmission electron microscopy （TEM）, respectively. The corrosion resistance was evaluated by electrochemical impedance spectroscopy （EIS）. The results showed that the adipic acid was absorbed at the electrolyte/anodic layer interface during anodizing. The corrosion rate of anodic film decreased and the film thickness increased. The film was uniform and compact especially at the film/substrate interface. After sealing procedure, anodic film formed with the addition of adipic acid exhibited improved dielectric property and corrosion resistance in aggressive environment.
文摘Using a laser detecting system, solubility data were measured for adipic acid dissolved in six pure solvents, namely, cyclohexanone, cyclohexanol, acetic acid, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethylsulfoxide at the temperature range from 293.15K to 353.15K. All these data were regressed by 2h, NRTL, Wilson, and the modified Wilson models. For the study of six, 2h, NRTL, and the modified Wilson models were found to provide an accurate mathematical representation of the experimental results, with overall average absolute relative deviations between measured and calculated values as 1.74%, 2.06%, and 3.06%, respectively. The results showed that the λh model is the most suitable for description of the solid-liquid equilibrium containing adipic acid.
基金financially supported by the National Natural Science Foundation of China(No.21304070)Natural Science Foundation of Tianjin City(No.15JCYBJC47300)+1 种基金Major Program of National Natural Science Foundation of China(No.11432016)the Municipal Key Program of Natural Science Foundation of Tianjin(No.14JCZDJC40700)
文摘Zinc phenylphosphonate （PPZn）, a benign and biocompatible nucleating agent, was prepared and incorporated into the biodegradable poly（ethylene adipate） （PEA） to investigate its effect on the crystallization behavior, crystallization kinetics and spherulite morphology of PEA. Upon addition of PPZn, the crystallization temperature and crystallinity of PEA in the non-isothermal crystallization process increased significantly. Analysis of crystallization kinetics by Avrami equation suggests that the crystallization time shortened greatly and crystallization rate increased markedly after addition of PPZn. In the presence of PPZn, the spherulite size decreased and spherulite density increased significantly. It suggests that PPZn is an efficient nucleating agent for the crystallization of PEA. The accelerated crystallization in the presence of PPZn is mainly attributed to the epitaxial nucleation of PEA crystals on the surface of PPZn crystals, that is, a perfect lattice matching between PEA crystal and PPZn crystal occurs.
文摘Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]heptane,trans/cis-cyclohexane-1,2-diol,cyclohex-2-en-1-ol,cyclohex-2-en-1-one,and even adipic acid.These products are broadly and abundantly used intermediates in the chemical industry;therefore,controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry,thus becoming the aim of synthetic and catalytic chemists in the field.Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance.This short review summarizes the recent advances on this subject,and the contents are mainly classified based on the chosen oxidants.We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.
基金Supported by the Natural Science Foundation of Henan Province (0511021700)
文摘Using a simple and reliable apparatus, the solubilities of adipic acid in water, ethanol, chloroform, n-butanol and acetone are determined by the analytic method. The results are correlated with λh equation, Apelblat equation, and UNIFAC equation. The solubilities calculated by these models are in good agreement with experi-mental data, so that the models can meet the requirements of engineering design.
文摘The reaction mechanism of the liquid phase ammoniation of adipic acid to adiponitrile was studied experimentally in a semi-batch reactor. Macrokinetics of the main and side reactions were identified to minimize corrosion and coking to prolong the operation period, to increase the yield of adiponitrile and to improve the design of the reactor. Macrokinetic equations of ammoniation-neutralization of adipic acid and dehydration were of first-order to adipic concentration cB≥3.5% and of second order for cB≥3.5%. Catalyst H3PO4 reduced the activation energy of neutralization and dehydration reactions of adipic acid and was significantly important for the second step of dehydration to produce adiponitrile.
基金supported by the National Natural Science Foundation(21706290)Natural Science Foundation of Shandong Province(ZR2017MB004,ZR2017BB007)+5 种基金Postdoctoral Research Funding of Shandong Province(201703016)Fundamental Research Funding of Qingdao(17-1-1-67-jch,17-1-1-80-jch)Qingdao Postdoctoral Research Funding(BY20170210)“the Fundamental Research Funds for the Central Universities”(18CX02145A,17CX02017A)new faculty start-up funding from China University of Petroleum(YJ201601058)China Postdoctoral Science Foundation(2017M612374)。
文摘Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses significant carbon footprint to the environment.Clean adipic acid synthesis methods using a heterogeneous catalyst with H2O2 as oxidant and water as solvent have potential advantages of low catalyst cost,easy synthesis and recovery,cleanness and environmental protection.In this work,hexagonal mesoporous silicate materials were synthesized by a sol–gel method and evaluated for cyclohexanol/cyclohexanone oxidation to adipic acid.The physical and chemical properties of Fe-HMS were characterized by XRD,HR-TEM,BET and UV–Vis.The experimental results showed that Fe-HMS materials show pore sizes ranging from 2–3 nm.W-and Mo-based polyoxometalates were also evaluated and compared to the Fe-based HMS catalysts.To improve the adipic acid yield,the influence of the transition metal as well as the effect of metal loading,reaction temperature and catalyst amount on the catalytic performances of Fe-HMS have been investigated in details.When Si/Fe atomic ratio=100,Fe-HMS catalyst shows the highest activity,with a cyclohexanone conversion of 92.3%and adipic acid selectivity of 29.4%.The reaction pathway of cyclohexanone oxidation was further proposed based on experimental data.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045 and 21276151)Natural Science Basic Research Plan in Shaanxi Province of China(No.2011JQ2004)Key Scientific Research Group of Shaanxi Province(No.2013KCT-08)
文摘The effects of crystallization temperature and blend ratio on the polymorphic crystal structures of poly（butylene adipate） （PBA） in poly（butylene succinate） （PBS）/poly（butylene adipate） （PBS/PBA） blends were studied by means of differential scanning calorimetry （DSC）, wide-angle X-ray diffraction （XRD） and atomic force microscopy （AFM）. It was revealed that the polymorphism of PBA can be regulated by the blend ratio even in a non-isothermal crystallization process. The results demonstrate that high temperature favors fiat-on α crystals, while low temperature contributes to edge-on β crystals. It was also found that the effect of blend ratio on the crystallization mechanism of PBA is well coincident with that of the crystallization temperature. The increment of PBS content in the PBS/PBA blend gives rise to more β-form crystals of PBA. For those PBS/PBA blends with low PBA content, the interlamellar phase segregation of PBA makes its molecular chains so difficult to diffuse from one isolated microdomain to another that high crystallization temperature and sufficiently long crystallization time will be required if the PBA α-type crystals are targeted.
基金financially supported by the National Natural Science Foundation of China(Nos.50833006,21274009,21204018,51221002and50973008)
文摘The crystallization behavior of poly（ethylene adipate） （PEA） on highly oriented high-density polyethylene （PE） substrate both from solution and isotropic melt was studied by means of optical microscopy, differential scanning calorimetry, atomic force microscopy and electron diffraction. The results show that the PE influences the crystallization of PEA strongly, which results in an epitaxial growth of PEA with well ordered structure. At the boundary of the PE substrate, a transcrystalline PEA layer is observed. Fine structural observation illustrates that the PEA grows on the PE substrate in edge- on lamellae with fixed orientation. Electron diffraction demonstrates that the epitaxial organization of PEA on PE occurs with both polymer chains parallel, which leads to the （00l） PEA diffractions inclined ±23.5° to the chain direction of PE crystals. Combining the real space morphological observation and electron diffraction results, it is concluded that the epitaxial PEA edge-on lamellae are folded in the {00l} lattice planes.
基金the Ningbo Science and Technology Plan Project (2018B10013)the Program of Shanghai Subject Chief Scientist (18XD1402000)。
文摘The adipic acid is an important intermediate in the production of nylon,polyurethane and polye ster resin s.The industrial approach for preparing adipic acid is through the liquid catalytic oxidation of KA oil with nitric acid.In this work,a comprehensive model is developed for this reaction based on the kinetic study conducted in a continuous flow tubular reactor.The kinetic model fits well with the experimental results across the experimental conditions,and the average relative error between the calculated and experimental values is 5.7%.Results show that there was an induction period at the early stage of reaction.Moreover,it is found that at temperature range of 328-358 K,the formation rate of adipic acid strongly dependents on the temperature and nitric acid concentration.The developed model is used to predict the yield of adipic acid at 359-368 K.The work in this study could provide much knowledge for industrial tubular reactor design.
基金Supported by the National Natural Science Foundation of China （21176070）.
文摘Based on the kinetic and thermodynamic equations, a comprehensive mathematical model for the con- tinuous esterification process of polyester polyols was developed, which was carried out in an innovational bub- bling reactive distillation tower （BRDT） at atmospheric pressure. In this new type of reactor, direct esterification between ethylene glycol and adipic acid was accomplished efficiently and rapidly. A bench BRDT with the height of 2 m was applied for the esteriflcation process of l^oly （ethylene adlpate） （P＇EA）. In the continuous operation, Hn- ear oligomers were discharged from the bottom of the column, while water passed a few column trays and a pack- ing section as a condensation byproduct. The influence of major operating conditions on reactor performance was also simulated. Simulation results were in good agreement with experimental data, providing a strategy for devel- oping and optimizing this process.
基金financially supported by the National Natural Science Foundation of China(No.51025314)the Oticon Foundation in Denmark
文摘Oriented and non-oriented Teflon films, which were found to have the same crystalline structure, but different surface morphologies, were used to sandwich poly（butylene adipate） （PBA） films during isothermal crystallization. It was found that both the Teflon surface structure and the PBA polymorphic structure are the determining factors to induce epitaxial crystallization. The oriented Teflon film was able to induce epitaxial crystallization of PBA α crystal, while the non-oriented Teflon did not induce any epitaxial crystallization of PBA. Epitaxial crystallization did not occurred for PBA β crystals between neither the oriented nor the non-oriented Teflon films. The enzymatic degradation rate of PBA films was not determined by the epitaxial crystallization, in fact it was still dependent on the polymorphic crystal structure of PBA. The morphological changes of PBA films after enzymatic degradation confirmed again that the epitaxial crystallization only occurred for the PBA film with α crystal structure which was produced by being sandwiched between oriented Teflon films, and it happened only on the surface of PBA films.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045,21276151)Key Scientific Research Group of Shanxi Province(No.2013KCT-08)Scientific Research Group of Shanxi University of Science and Technology(No.TD12-04)
文摘The miscibility, isothermal crystallization kinetics and morphology of the poly（vinylidene fluoride）（PVDF）/poly（ethylene adipate）（PEA） blends have been studied by differential scanning calorimetry（DSC）, optical microscopy（OM） and scanning electron microscopy（SEM）. A depression of the equilibrium melting point of PVDF was observed. From the melting point data of PVDF, a negative but quite small value of the interaction parameter ？PVDF-PEA is derived using the Flory-Huggins equation, implying that PVDF shows miscibility with PEA to some extent. Nonisothermal and isothermal crystallization kinetics suggest that the crystallization rate of PVDF decreases with increasing the amount of PEA, and a contrary trend was found when PEA crystallizes with the increase of the amount of PVDF. It was further disclosed that the blend ratio and crystallization temperature affect the texture of PVDF spherulites greatly, which determines the subsequent crystallization of PEA. At high temperatures, e.g. 150 ℃, the band spacing of PVDF spherulites increases with the addition of PEA content and the spherulitic structure becomes more open. In this case, spherulitic crystallization of PEA is not observed for all blend compositions. At low temperatures, e.g. 130 ℃, for the PEA-rich blends, the interpenetrated structures are eventually formed by the penetration of the spherulites of PEA growing within the pre-existing PVDF spherulites.
基金financially supported by the National Natural Science Foundation of China(Nos.21204045 and 21276151)Key Scientific Research Group of Shanxi Province(No.2013KCT-08)Scientific Research Group of Shanxi University of Science and Technology(No.TD12-04)
文摘The effects of PEA on the ）γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy （OM）, infrared spectroscopy （IR） and scanning electron microscopy （SEM）. The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within theγ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.
基金financial support by the Ministry of Science and Technology of China (Grant No.2018YFC1509006)the National Natural Science Foundation of China (Grant No.71874096)+1 种基金the Macao SAR Government Higher Education Fundthe Macao University of Science and Technology (Grant No.FRG-19-008-MSB)。
文摘Adipic acid is an important petrochemical product,and its production process emits a high concentration of greenhouse gas N_2 O.This paper aims to provide quantitative references for relevant authorities to formulate greenhouse gas control roadmaps.The forecasting method of this paper is consistent with the published national inventory in terms of caliber.Based on the N_2 O abatement technical parameters of adipic acid and the production trend,this paper combines the scenario analysis and provides a measurement of comprehensive N_2 O abatement effect of the entire industry in China.Four future scenarios are assumed.The baseline scenario(BAUS) is a frozen scenario.Three emission abatement scenarios(ANAS,SNAS,and ENAS) are assumed under different strength of abatement driving parameters.The results show that China's adipic acid production process can achieve increasingly significant N_2 O emission abatement effects.Compared to the baseline scenario,by 2030,the N_2 O emission abatements of the three emission abatement scenarios can reach 207-399 kt and the emission abatement ratios can reach 32.5%-62.6%.By 2050,the N_2 O emission abatements for the three emission abatement scenarios can reach 387-540 kt and the emission abatement ratios can reach 71.4%-99.6%.
