This wok proposed the extraction distillation coupled pervaporation(ED+PV) technology process using two different solvents to separate isopropanol(IPA) and diisopropyl ether(DIPE) from DIPE/IPA/H_(2)O ternary heteroge...This wok proposed the extraction distillation coupled pervaporation(ED+PV) technology process using two different solvents to separate isopropanol(IPA) and diisopropyl ether(DIPE) from DIPE/IPA/H_(2)O ternary heterogeneous azeotropes in industrial wastewater from the synthesis of isopropanol in this study.Based on strict design specifications, simulation and sequential iteration methods are used for process design and optimization. Compared to the ethylene glycol(EG)-EG+H_(2)O process and the 1,3-propanediol(PDO)-IPA+H_(2)O process, the total annual cost(TAC) of the EG-IPA+H_(2)O process decreased by 20.76% and 7.86%(PDO). Compared to the EG-EG+H_(2)O process, the TAC of the PDO-IPA+H_(2)O process reduced 14%, but the global warming potential(GWP) and human toxicity of the PDO-IPA+H_(2)O process increased 11.3% and 4.07% respectively. Compared to the PDO-IPA+H_(2)O process, the EG-IPA+H_(2)O process saves 7.86%(TAC), 9.78%(GWP) and 9.85%(human toxicity). The ED+PV process with EG is superior to PDO in factors of TAC, energy consumption, human toxicity and environment. The EG-IPA+H_(2)O process changed the separation order of the products of the multi-azeotropic system, reduced the cost and energy conservation of the system, and enhanced the environmental protection evaluation of the process, is the best process through life cycle assessment for analyzing the economy, energy conservation, environmental assessment and human toxicity, designing cleaner products, controlling waste discharge, and promoting the chemical purification industry. This work provides a new process design and optimized separation ideas, will have a good guiding significance for the research and application separation of multi-azeotropic mixture with mixed solvents in organic wastewater from the cleaner chemical production, has been up to standard wastewater discharge process, and realized the development goal of carbon peak and carbon neutrality in the sustainable development of chemical clean industry.展开更多
For a long time,China's regional water resource imbalance has restricted the development of coal chemical industry,and it is imperative to achieve zero liquid discharge(ZLD).Therefore,the game relationship between...For a long time,China's regional water resource imbalance has restricted the development of coal chemical industry,and it is imperative to achieve zero liquid discharge(ZLD).Therefore,the game relationship between technical indicators,costs and emissions in ZLD process of fixed-bed coal gasification wastewater treatment process should be explored in detail.According to the accurate model,the simulation for ZLD of fixed-bed coal gasification wastewater treatment process is established,and this process is assessed from the perspective of thermodynamics,economy,and environment.The total energy consumption of ZLD process before optimization is 4.032×10^(8)W.The results of exergy analysis show exergy destruction of ZLD process is 94.55%.For economic and environmental results,the total annual cost is 1.892×10^(7)USD·a^(-1)and the total environmental impact is 4.782×10^(-8).The total energy consumption of the optimal six-step ZLD process based on multi-objective optimization is 4.028×10^(8)W.The CO_(2)content in the treated wastewater is 0.1%.This study will have an important role in promoting the establishment of the ZLD process for coal chemistry industry.展开更多
In this study,the effects of intermetallic compounds(Mg_(17)Al_(12)and Al_(8)Mn_(5))on the Mg-Al layered double hydroxide(LDH)formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)_(2)steam coatings on AZ...In this study,the effects of intermetallic compounds(Mg_(17)Al_(12)and Al_(8)Mn_(5))on the Mg-Al layered double hydroxide(LDH)formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)_(2)steam coatings on AZ80 Mg alloy were investigated.Citric acid(CA)was used to activate the alloy surface during the pretreatment process.The alloy was first pretreated with CA and then subjected to a hydrothermal process using ultrapure water to produce Mg-Al-LDH/Mg(OH)_(2)steam coating.The effect of different time of acid pretreatment on the activation of the intermetallic compounds was investigated.The microstructure and elemental composition of the obtained coatings were analyzed using FE-SEM,EDS,XRD and FT-IR.The corrosion resistance of the coated samples was evaluated using different techniques,i.e.,potentiodynamic polarization(PDP),electrochemical impedance spectrum(EIS)and hydrogen evolution test.The results indicated that the CA pretreatment significantly influenced the activity of the alloy surface by exposing the intermetallic compounds.The surface area fraction of Mg_(17)Al_(12)and Al_(8)Mn_(5)phases on the surface of the alloy was significantly higher after the CA pretreatment,and thus promoted the growth of the subsequent Mg-Al-LDH coatings.The CA pretreatment for 30 s resulted in a denser and thicker LDH coating.Increase in the CA pretreatment time significantly led to the improvement in corrosion resistance of the coated AZ80 alloy.The corrosion current density of the coated alloy was lower by three orders of magnitude as compared to the uncoated alloy.展开更多
A large amount of waste liquids containing methanol/acetone/water mixtures are produced in the synthesis of methyl methacrylate(MMA).Under the advocacy of green chemical industry,it is urgent to develop an efficient,e...A large amount of waste liquids containing methanol/acetone/water mixtures are produced in the synthesis of methyl methacrylate(MMA).Under the advocacy of green chemical industry,it is urgent to develop an efficient,economic and energy-saving mixture separation process.Through thermodynamic azeotropic behavior and pressure sensitivity analysis,pressure-swing distillation was determined and the optimal separation pressure of each column in the process was obtained.Due to the composition of waste liquids produced were quite different in MMA production,the pressure-swing distillation separation process was designed to fully achieve the accurate waste liquids treatment.Taking the total annual cost(TAC)as the target,the sequential iteration method was used to optimize the process,and the impact of composition on economy was compared.In order to further realize the energy-saving of the separation process,the pervaporation membrane module was introduced to pretreat the waste liquid in the pressure-swing distillation.The results showed that the TAC of the coupling process was 46% higher than that of the pressure-swing distillation process,and the thermodynamic efficiency was 30% higher.This study provides waste liquid treatment technology for enterprises and analyzes its economic and energy efficiency,which has reference significance for the development of coupled separation technology.展开更多
Aimed at the current treatment status of the polymer-flooding wastewater in Bohai oilfield, electrochemical technology used for polymer-degradation and oil-removal was researched. It formed the process flow of cyclone...Aimed at the current treatment status of the polymer-flooding wastewater in Bohai oilfield, electrochemical technology used for polymer-degradation and oil-removal was researched. It formed the process flow of cyclone mixed dosing → electrochemical removal oil → inclined tube removal oil → walnut shell filter, and a set of skid mounted wastewater containing polymer treatment plant was designed and manufactured, which was used for the field test of electrochemical treatment of wastewater containing polymer in offshore oilfield. The result shows that the oil removal rate of the electrochemical treatment process is over 98%, and the synergistic effect is significant especially used in conjunction with water clarifier of BHQ-04. When the amount of water clarifier is 50 - 150 mg/L, the oil content, the median particle diameter and the suspended solids content of the filtered water is 8 - 18 mg/L, 1.9 - 2.26 μm and 1.39 - 2.04 mg/L respectively, which reach the scene water quality standards for water injection.展开更多
Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practic...Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe0 (160–200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO(OH), was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO(OH) increased as reaction time went on, whereas the proportion of Fe3O4 decreased.展开更多
Design and control of pressure-swing distillation(PSD) with different heat integration modes for the separation of methyl acetate/methanol azeotrope are explored using Aspen Plus and Aspen Dynamics. First, an optimum ...Design and control of pressure-swing distillation(PSD) with different heat integration modes for the separation of methyl acetate/methanol azeotrope are explored using Aspen Plus and Aspen Dynamics. First, an optimum steady-state separation configuration conditions are obtained via taking the total annual cost(TAC) or total reboiler heat duty as the objective functions. The results show that about 27.68% and 25.40% saving in TAC can be achieved by the PSD with full and partial heat integration compared to PSD without heat integration. Second,temperature control tray locations are obtained according to the sensitivity criterion and singular value decomposition(SVD) analysis and the single-end control structure is effective based on the feed composition sensitivity analysis. Finally, the comparison of dynamic controllability is made among various control structures for PSD with partial and full heat integration. It is shown that both control structures of composition/temperature cascade and pressure-compensated temperature have a good dynamic response performance for PSD with heat integration facing feed flowrate and composition disturbances. However, PSD with full heat integration performs the poor controllability despite of a little bit of economy.展开更多
Mine dust is classified as one of five natural coal mining disasters because it can harm the health of miners and poses a serious threat to the safety of the coal mine. Therefore, preparation of an effective dust supp...Mine dust is classified as one of five natural coal mining disasters because it can harm the health of miners and poses a serious threat to the safety of the coal mine. Therefore, preparation of an effective dust suppression agent is highly desired. To improve the capture efficiency of fine dust, this study examines the dust suppression effects of various combinations of wetting agents, additives, and coagulation agents by using the optimum seeking method to reduce mine dust, particularly respirable particles. The optimal formula is shown to contain 10wt% fatty alcohol polyoxyethylene ether(JFC), 4.96wt% cationic polyacrylamide, and 4wt% calcium chloride. The dust suppression effect can be achieved at 96.1% in 5 min by using the optimal formula.展开更多
A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential therma...A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.展开更多
Spatial variation of dissolved organic carbon(DOC) in soils of riparian wetlands and responses to hydro-geomorphologic changes in the Sanjiang Plain were analyzed through in situ collecting soil samples in the Naoli R...Spatial variation of dissolved organic carbon(DOC) in soils of riparian wetlands and responses to hydro-geomorphologic changes in the Sanjiang Plain were analyzed through in situ collecting soil samples in the Naoli River and the Bielahong River. The results showed that the average contents of DOC for soil layer of 0–100 cm were 730.6 mg/kg, 250.9 mg/kg, 423.0 mg/kg and 333.1 mg/kg respectively from riverbed to river terrace along the transverse directions of the Naoli watershed. The content of the soil DOC was the highest in the riverbed, lower in the high floodplain and much lower in the river terrace, and it was the lowest in the low floodplain. The difference in the content and vertical distribution of DOC between the riverbed and the three riparian wetlands was significant, while it was not significant among the low floodplain, the high floodplain and the river terrace. The variability of soil DOC was related to the hydrological connectivity between different landscape position of the riparian wetlands and the adjacent stream. Extremely significant correlations were observed between DOC and total organic carbon(TOC), total iron(TFe), ferrous iron(Fe(II)) whose correlation coefficients were 0.819, –0.544 and –0.709 in riparian wetlands of the Naoli River. With the increase of wetland destruction, soil p H increased and soil DOC content changed. The correlation coefficients between soil DOC and TOC, TFe, Fe(II) also changed into 0.759, –0.686 and –0.575 respectively in the Bielahong River. Under the impact of drainage ditches, the correlations between soil DOC and TFe, Fe(II) were not obvious, while the soil p H was weakly alkaline and was negatively correlated with soil DOC in the previous high floodplain. It indicates that riparian hydro-geomorphology is the main factor that could well explain this spatial variability of soil DOC, and the agricultural environmental hydraulic works like ditching also must be considered.展开更多
According to the Van Uitert experimental equation, crystal-lattice environment of Eu2+ in the Sr4Si3O8Cl4 crystal was discussed. By adding Mg2+ to the host lattice, Sr4- x Mg x Si3O8Cl4∶Eu2+ was synthesized and the e...According to the Van Uitert experimental equation, crystal-lattice environment of Eu2+ in the Sr4Si3O8Cl4 crystal was discussed. By adding Mg2+ to the host lattice, Sr4- x Mg x Si3O8Cl4∶Eu2+ was synthesized and the emission peak shifted from blue-green （488 nm） to blue-violet （411 nm） with the increase of amount of the magnesium which replaced the strontium. By analyzing the spectra of Sr4- x Mg x Si3O8Cl4∶Eu2+ the two Eu2+ emission centers were found because of the change of crystal-lattice environment in the host and the crystal structure was obtained by X-ray diffraction data.展开更多
A field experiment of 2-year-old gentian (Gentiana manshurica Kitag.) with application of boron (B), zinc (Zn), and iron (Fe) in Taikang County, Heilongjiang Province, was conducted to study the effects of the three m...A field experiment of 2-year-old gentian (Gentiana manshurica Kitag.) with application of boron (B), zinc (Zn), and iron (Fe) in Taikang County, Heilongjiang Province, was conducted to study the effects of the three microelements on gentiopicroside content in the roots of gentian, uptake of these elements, and root dry weight as well as the ratio of root dry weight to fresh weight. Zinc sulfate, ferrous sulfate, and borax were split sprinkled on 2-year-old gentian on June 26, July 18, and August 25, 2002, with sprinkling water taken as a control. Compared with the control, applying B significantly increased (P < 0.05) the gentiopicroside content by 7.9%, and there was a highly significant increase of 22.4% (P < 0.01) in the root dry weight. Meanwhile, B content in the shoots of gentian gradually increased from the vegetative to the harvesting period, while Fe decreased at first and then increased. Fe treatment increased the gentiopicroside content only by 4.0% and the content was slightly decreased by the Zn treatment (3.1%) as compared to the control. The three microelements had different effects on the gentiopicroside content and appropriate microelement application could increase active ingredient content of gentian.展开更多
Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing l...Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing lower alcohols. Experimental techniques and ab initio approaches can produce accurate results;however, these two processes are time consuming and labor intensive. Although thermodynamic equations such as UNIFAC are widely used, experimental values are required, and it is difficult to choose the best groups to represent a complex system. Because of their high efficiency and fast calculation speed, quantitative structure–property relationship(QSPR) tools were used in this work to predict the azeotropic temperatures and compositions of binary azeotropes containing lower alcohols. The QSPR models for 64 binary azeotropes based on centroid approximation and weighted-contribution-factor approximation were established using the genetic function approximation(GFA) procedure in Materials Studio software, and a leave-one-out cross-validation procedure was conducted.External tests of an additional 16 azeotropes were also investigated, and high determination coefficient values were obtained. The best QSPR models were explained in terms of the molecular structure of the azeotropes,and good predictive ability was obtained within acceptable prediction error levels.展开更多
The synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide using potassium hydroxide as catalyst in the presence of CH3I and the effect of ionic liquid on the reaction were investigated. The results sh...The synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide using potassium hydroxide as catalyst in the presence of CH3I and the effect of ionic liquid on the reaction were investigated. The results showed that KOH is an effective catalyst; the high selectivity and raised yield of DMC formation under mild conditions were achieved. However, the addition of the ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), can evidently accelerate the conversion of methanol and yield of the product.展开更多
The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were i...The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).展开更多
In order to improve the ability of ozone to catalyze the degradation of phenolic pollutants in wastewater,the CuO/Al2O3 catalysts was prepared by the impregnation precipitation method and an ozone catalytic oxidation ...In order to improve the ability of ozone to catalyze the degradation of phenolic pollutants in wastewater,the CuO/Al2O3 catalysts was prepared by the impregnation precipitation method and an ozone catalytic oxidation system was constructed.The actual phenolic sewage was used as the treatment object.And the reaction conditions of the system were optimized,and the treatment effect was determined,while the non-catalytic system was used as a control group.At the same time,the influence of salt and ammonia nitrogen related water quality on the system was studied.The optimal reaction conditions for the treatment of phenolic wastewater covered:a catalyst dosage of 30 g/L,an ozone flow rate of 0.3 m3/h,a pH value of 8.80,and a reaction time of 15 minutes.Under these conditions,the phenol and COD removal rates of the system reached 98.7%and 49.4%,respectively,which were by 31.3 percentage points and 16.2 percentage points higher than that of the ozonation system alone.The salt and ammonia nitrogen in the sewage can reduce the oxidation effect of the system.When the salinity reached 10%and the ammonia nitrogen content reached 13 000 mg/L,the removal rate of phenol could be reduced by about 20%.The results of this paper have a reference value for phenol wastewater treatment engineering.展开更多
Amorphous 2,4,6-trissubstituted pyridines containing three peripheral carbazole or two triphenylarnine and one carbazole moieties,respectively,have been synthesized and characterized.The properties of the compounds ar...Amorphous 2,4,6-trissubstituted pyridines containing three peripheral carbazole or two triphenylarnine and one carbazole moieties,respectively,have been synthesized and characterized.The properties of the compounds are investigated by UV-vis absorption,photoluminescence spectroscopy,thermal analysis as well as cyclic voltammetry.The results show that the compounds have high thermal stability,emit blue light.Also,the compounds possess the HOMO and LUMO energy levels comparable to those of NPB.The effects of different substituents on the electronic properties of the materials have been discussed.展开更多
In the process of liquid-liquid extraction,it is necessary to look for green solvents as extractants.Ionic liquids have been studied as extractants due to their green recyclability in recent years.The infinite dilutio...In the process of liquid-liquid extraction,it is necessary to look for green solvents as extractants.Ionic liquids have been studied as extractants due to their green recyclability in recent years.The infinite dilution activity coefficients of 100 ionic liquids with a combination of 10 cations and 10 anions were calculated by COSMO-SAC model,and theσ-profiles were plotted.The distribution coefficient and separation coefficient of n-heptane+tert-butanol+ILs were determined.[OMIM][OTF],[HMIM][OTF]and[BMIM][OTF]were selected as solvents for this study.The interaction energy,bond length and charge density of ionic liquids with tert-butanol were calculated by quantum chemistry calculation method.According to these results,the rationality of selected ionic liquids as extractants could be analyzed from the molecular level.At 298.15 K and 101.325 kPa,the liquid-liquid equilibrium data of the ternary system{n-heptane+tert-butanol+[OMIM][OTF],nheptane+tert-butanol+[BMIM][OTF],n-heptane+tert-butanol+[HMIM][OTF]}were measured.The distribution coefficient and separation coefficient for judging the extraction effect were obtained.The NRTL model was used to correlate liquid-liquid equilibrium experimental data,and correlation result proved that the correlated and experimental data had a good correlation.The research on ionic liquids is of great significance to the development of green and sustainable chemical industry.展开更多
基金supported by the National Natural Science Foundation of China (21776145 and 21808117)。
文摘This wok proposed the extraction distillation coupled pervaporation(ED+PV) technology process using two different solvents to separate isopropanol(IPA) and diisopropyl ether(DIPE) from DIPE/IPA/H_(2)O ternary heterogeneous azeotropes in industrial wastewater from the synthesis of isopropanol in this study.Based on strict design specifications, simulation and sequential iteration methods are used for process design and optimization. Compared to the ethylene glycol(EG)-EG+H_(2)O process and the 1,3-propanediol(PDO)-IPA+H_(2)O process, the total annual cost(TAC) of the EG-IPA+H_(2)O process decreased by 20.76% and 7.86%(PDO). Compared to the EG-EG+H_(2)O process, the TAC of the PDO-IPA+H_(2)O process reduced 14%, but the global warming potential(GWP) and human toxicity of the PDO-IPA+H_(2)O process increased 11.3% and 4.07% respectively. Compared to the PDO-IPA+H_(2)O process, the EG-IPA+H_(2)O process saves 7.86%(TAC), 9.78%(GWP) and 9.85%(human toxicity). The ED+PV process with EG is superior to PDO in factors of TAC, energy consumption, human toxicity and environment. The EG-IPA+H_(2)O process changed the separation order of the products of the multi-azeotropic system, reduced the cost and energy conservation of the system, and enhanced the environmental protection evaluation of the process, is the best process through life cycle assessment for analyzing the economy, energy conservation, environmental assessment and human toxicity, designing cleaner products, controlling waste discharge, and promoting the chemical purification industry. This work provides a new process design and optimized separation ideas, will have a good guiding significance for the research and application separation of multi-azeotropic mixture with mixed solvents in organic wastewater from the cleaner chemical production, has been up to standard wastewater discharge process, and realized the development goal of carbon peak and carbon neutrality in the sustainable development of chemical clean industry.
基金supported by the National Natural Science Foundation of China(22078166,22178188)。
文摘For a long time,China's regional water resource imbalance has restricted the development of coal chemical industry,and it is imperative to achieve zero liquid discharge(ZLD).Therefore,the game relationship between technical indicators,costs and emissions in ZLD process of fixed-bed coal gasification wastewater treatment process should be explored in detail.According to the accurate model,the simulation for ZLD of fixed-bed coal gasification wastewater treatment process is established,and this process is assessed from the perspective of thermodynamics,economy,and environment.The total energy consumption of ZLD process before optimization is 4.032×10^(8)W.The results of exergy analysis show exergy destruction of ZLD process is 94.55%.For economic and environmental results,the total annual cost is 1.892×10^(7)USD·a^(-1)and the total environmental impact is 4.782×10^(-8).The total energy consumption of the optimal six-step ZLD process based on multi-objective optimization is 4.028×10^(8)W.The CO_(2)content in the treated wastewater is 0.1%.This study will have an important role in promoting the establishment of the ZLD process for coal chemistry industry.
基金This work was supported by the National Natural Science Foundation of China(Grant Nos.51601108 and 52071191)the Natural Science Foundation of Shandong Province(ZR2020ME011).
文摘In this study,the effects of intermetallic compounds(Mg_(17)Al_(12)and Al_(8)Mn_(5))on the Mg-Al layered double hydroxide(LDH)formation mechanism and corrosion behavior of an in-situ LDH/Mg(OH)_(2)steam coatings on AZ80 Mg alloy were investigated.Citric acid(CA)was used to activate the alloy surface during the pretreatment process.The alloy was first pretreated with CA and then subjected to a hydrothermal process using ultrapure water to produce Mg-Al-LDH/Mg(OH)_(2)steam coating.The effect of different time of acid pretreatment on the activation of the intermetallic compounds was investigated.The microstructure and elemental composition of the obtained coatings were analyzed using FE-SEM,EDS,XRD and FT-IR.The corrosion resistance of the coated samples was evaluated using different techniques,i.e.,potentiodynamic polarization(PDP),electrochemical impedance spectrum(EIS)and hydrogen evolution test.The results indicated that the CA pretreatment significantly influenced the activity of the alloy surface by exposing the intermetallic compounds.The surface area fraction of Mg_(17)Al_(12)and Al_(8)Mn_(5)phases on the surface of the alloy was significantly higher after the CA pretreatment,and thus promoted the growth of the subsequent Mg-Al-LDH coatings.The CA pretreatment for 30 s resulted in a denser and thicker LDH coating.Increase in the CA pretreatment time significantly led to the improvement in corrosion resistance of the coated AZ80 alloy.The corrosion current density of the coated alloy was lower by three orders of magnitude as compared to the uncoated alloy.
基金supported by the National Natural Science Foundation of China(22078166)。
文摘A large amount of waste liquids containing methanol/acetone/water mixtures are produced in the synthesis of methyl methacrylate(MMA).Under the advocacy of green chemical industry,it is urgent to develop an efficient,economic and energy-saving mixture separation process.Through thermodynamic azeotropic behavior and pressure sensitivity analysis,pressure-swing distillation was determined and the optimal separation pressure of each column in the process was obtained.Due to the composition of waste liquids produced were quite different in MMA production,the pressure-swing distillation separation process was designed to fully achieve the accurate waste liquids treatment.Taking the total annual cost(TAC)as the target,the sequential iteration method was used to optimize the process,and the impact of composition on economy was compared.In order to further realize the energy-saving of the separation process,the pervaporation membrane module was introduced to pretreat the waste liquid in the pressure-swing distillation.The results showed that the TAC of the coupling process was 46% higher than that of the pressure-swing distillation process,and the thermodynamic efficiency was 30% higher.This study provides waste liquid treatment technology for enterprises and analyzes its economic and energy efficiency,which has reference significance for the development of coupled separation technology.
文摘Aimed at the current treatment status of the polymer-flooding wastewater in Bohai oilfield, electrochemical technology used for polymer-degradation and oil-removal was researched. It formed the process flow of cyclone mixed dosing → electrochemical removal oil → inclined tube removal oil → walnut shell filter, and a set of skid mounted wastewater containing polymer treatment plant was designed and manufactured, which was used for the field test of electrochemical treatment of wastewater containing polymer in offshore oilfield. The result shows that the oil removal rate of the electrochemical treatment process is over 98%, and the synergistic effect is significant especially used in conjunction with water clarifier of BHQ-04. When the amount of water clarifier is 50 - 150 mg/L, the oil content, the median particle diameter and the suspended solids content of the filtered water is 8 - 18 mg/L, 1.9 - 2.26 μm and 1.39 - 2.04 mg/L respectively, which reach the scene water quality standards for water injection.
基金supported by the Development Program for Outstanding Young Teachers in Harbin Institute of Technology (No. HITQNJS. 2007. 038)
文摘Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe0 (160–200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO(OH), was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO(OH) increased as reaction time went on, whereas the proportion of Fe3O4 decreased.
文摘Design and control of pressure-swing distillation(PSD) with different heat integration modes for the separation of methyl acetate/methanol azeotrope are explored using Aspen Plus and Aspen Dynamics. First, an optimum steady-state separation configuration conditions are obtained via taking the total annual cost(TAC) or total reboiler heat duty as the objective functions. The results show that about 27.68% and 25.40% saving in TAC can be achieved by the PSD with full and partial heat integration compared to PSD without heat integration. Second,temperature control tray locations are obtained according to the sensitivity criterion and singular value decomposition(SVD) analysis and the single-end control structure is effective based on the feed composition sensitivity analysis. Finally, the comparison of dynamic controllability is made among various control structures for PSD with partial and full heat integration. It is shown that both control structures of composition/temperature cascade and pressure-compensated temperature have a good dynamic response performance for PSD with heat integration facing feed flowrate and composition disturbances. However, PSD with full heat integration performs the poor controllability despite of a little bit of economy.
基金National Natural Science Funds-Coal Joint Funds Key Support Project (No. U1261205)Basic Research Plan Project of Science and Technology of Qingdao (No. 13-1-4-149-jch)Key Technology Development Projects of Qingdao Economic and Technological Development Zone (No. 2013-1-66) for providing the financial support to this research
文摘Mine dust is classified as one of five natural coal mining disasters because it can harm the health of miners and poses a serious threat to the safety of the coal mine. Therefore, preparation of an effective dust suppression agent is highly desired. To improve the capture efficiency of fine dust, this study examines the dust suppression effects of various combinations of wetting agents, additives, and coagulation agents by using the optimum seeking method to reduce mine dust, particularly respirable particles. The optimal formula is shown to contain 10wt% fatty alcohol polyoxyethylene ether(JFC), 4.96wt% cationic polyacrylamide, and 4wt% calcium chloride. The dust suppression effect can be achieved at 96.1% in 5 min by using the optimal formula.
基金Project supported by the Knowledge Innovation Engineering Project of the Chinese Academy of Sciences(No. KSCX2-YW-N-46-06)the National Natural Science Foundation of China(No. 40501030).
基金Supported by the National Natural Science Foundation of China（21161009）the Natural Science Foundation of Jiangxi Province（20122BAB213001,20114BAB213002）the Science and Technology Foundation of Jiangxi Province（GJJ11613）
文摘A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.
基金Under the auspices of National Natural Science Foundation of China(No.41101080,41171047)Natural Science Foundation of Shandong Province(No.ZR2014DQ028)
文摘Spatial variation of dissolved organic carbon(DOC) in soils of riparian wetlands and responses to hydro-geomorphologic changes in the Sanjiang Plain were analyzed through in situ collecting soil samples in the Naoli River and the Bielahong River. The results showed that the average contents of DOC for soil layer of 0–100 cm were 730.6 mg/kg, 250.9 mg/kg, 423.0 mg/kg and 333.1 mg/kg respectively from riverbed to river terrace along the transverse directions of the Naoli watershed. The content of the soil DOC was the highest in the riverbed, lower in the high floodplain and much lower in the river terrace, and it was the lowest in the low floodplain. The difference in the content and vertical distribution of DOC between the riverbed and the three riparian wetlands was significant, while it was not significant among the low floodplain, the high floodplain and the river terrace. The variability of soil DOC was related to the hydrological connectivity between different landscape position of the riparian wetlands and the adjacent stream. Extremely significant correlations were observed between DOC and total organic carbon(TOC), total iron(TFe), ferrous iron(Fe(II)) whose correlation coefficients were 0.819, –0.544 and –0.709 in riparian wetlands of the Naoli River. With the increase of wetland destruction, soil p H increased and soil DOC content changed. The correlation coefficients between soil DOC and TOC, TFe, Fe(II) also changed into 0.759, –0.686 and –0.575 respectively in the Bielahong River. Under the impact of drainage ditches, the correlations between soil DOC and TFe, Fe(II) were not obvious, while the soil p H was weakly alkaline and was negatively correlated with soil DOC in the previous high floodplain. It indicates that riparian hydro-geomorphology is the main factor that could well explain this spatial variability of soil DOC, and the agricultural environmental hydraulic works like ditching also must be considered.
文摘According to the Van Uitert experimental equation, crystal-lattice environment of Eu2+ in the Sr4Si3O8Cl4 crystal was discussed. By adding Mg2+ to the host lattice, Sr4- x Mg x Si3O8Cl4∶Eu2+ was synthesized and the emission peak shifted from blue-green （488 nm） to blue-violet （411 nm） with the increase of amount of the magnesium which replaced the strontium. By analyzing the spectra of Sr4- x Mg x Si3O8Cl4∶Eu2+ the two Eu2+ emission centers were found because of the change of crystal-lattice environment in the host and the crystal structure was obtained by X-ray diffraction data.
基金Project supported by the Key Technologies Research and Development Program of Heilongjiang Province (No. GC01C405-02).
文摘A field experiment of 2-year-old gentian (Gentiana manshurica Kitag.) with application of boron (B), zinc (Zn), and iron (Fe) in Taikang County, Heilongjiang Province, was conducted to study the effects of the three microelements on gentiopicroside content in the roots of gentian, uptake of these elements, and root dry weight as well as the ratio of root dry weight to fresh weight. Zinc sulfate, ferrous sulfate, and borax were split sprinkled on 2-year-old gentian on June 26, July 18, and August 25, 2002, with sprinkling water taken as a control. Compared with the control, applying B significantly increased (P < 0.05) the gentiopicroside content by 7.9%, and there was a highly significant increase of 22.4% (P < 0.01) in the root dry weight. Meanwhile, B content in the shoots of gentian gradually increased from the vegetative to the harvesting period, while Fe decreased at first and then increased. Fe treatment increased the gentiopicroside content only by 4.0% and the content was slightly decreased by the Zn treatment (3.1%) as compared to the control. The three microelements had different effects on the gentiopicroside content and appropriate microelement application could increase active ingredient content of gentian.
基金Supported by the National Natural Science Foundation of China(21776145,21676152)Key Research Project of Shandong Province(2016GSF116004)
文摘Binary azeotropes, which contain two chemicals with a relative volatility of 1, are very common in the chemical industry. Understanding azeotropes is essential for effectively separating binary azeotropes containing lower alcohols. Experimental techniques and ab initio approaches can produce accurate results;however, these two processes are time consuming and labor intensive. Although thermodynamic equations such as UNIFAC are widely used, experimental values are required, and it is difficult to choose the best groups to represent a complex system. Because of their high efficiency and fast calculation speed, quantitative structure–property relationship(QSPR) tools were used in this work to predict the azeotropic temperatures and compositions of binary azeotropes containing lower alcohols. The QSPR models for 64 binary azeotropes based on centroid approximation and weighted-contribution-factor approximation were established using the genetic function approximation(GFA) procedure in Materials Studio software, and a leave-one-out cross-validation procedure was conducted.External tests of an additional 16 azeotropes were also investigated, and high determination coefficient values were obtained. The best QSPR models were explained in terms of the molecular structure of the azeotropes,and good predictive ability was obtained within acceptable prediction error levels.
文摘The synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide using potassium hydroxide as catalyst in the presence of CH3I and the effect of ionic liquid on the reaction were investigated. The results showed that KOH is an effective catalyst; the high selectivity and raised yield of DMC formation under mild conditions were achieved. However, the addition of the ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), can evidently accelerate the conversion of methanol and yield of the product.
基金supported by the National Natural Science Foundation of China(No.51876080)the Strategic International Scientific and Technological Innovation Cooperation Special Funds of National Key Research and Development Program of China(No.2016YFE0204000)+3 种基金the Program for Taishan Scholars of Shandong Province Governmentthe Recruitment Program of Global Experts(Thousand Youth Talents Plan)the Natural Science Foundation of Shandong Province(ZR2017BB002)the Key Research and Development Program of Shandong Province(2018GSF116014)。
文摘The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).
基金financially supported by the Ministry of Science and Technology of the People’s Republic of China [Grant No. 2017YFC1404605]
文摘In order to improve the ability of ozone to catalyze the degradation of phenolic pollutants in wastewater,the CuO/Al2O3 catalysts was prepared by the impregnation precipitation method and an ozone catalytic oxidation system was constructed.The actual phenolic sewage was used as the treatment object.And the reaction conditions of the system were optimized,and the treatment effect was determined,while the non-catalytic system was used as a control group.At the same time,the influence of salt and ammonia nitrogen related water quality on the system was studied.The optimal reaction conditions for the treatment of phenolic wastewater covered:a catalyst dosage of 30 g/L,an ozone flow rate of 0.3 m3/h,a pH value of 8.80,and a reaction time of 15 minutes.Under these conditions,the phenol and COD removal rates of the system reached 98.7%and 49.4%,respectively,which were by 31.3 percentage points and 16.2 percentage points higher than that of the ozonation system alone.The salt and ammonia nitrogen in the sewage can reduce the oxidation effect of the system.When the salinity reached 10%and the ammonia nitrogen content reached 13 000 mg/L,the removal rate of phenol could be reduced by about 20%.The results of this paper have a reference value for phenol wastewater treatment engineering.
文摘Amorphous 2,4,6-trissubstituted pyridines containing three peripheral carbazole or two triphenylarnine and one carbazole moieties,respectively,have been synthesized and characterized.The properties of the compounds are investigated by UV-vis absorption,photoluminescence spectroscopy,thermal analysis as well as cyclic voltammetry.The results show that the compounds have high thermal stability,emit blue light.Also,the compounds possess the HOMO and LUMO energy levels comparable to those of NPB.The effects of different substituents on the electronic properties of the materials have been discussed.
基金supported by National Natural Science Foundation of China(No.21776145 and No.21676152)Qingdao science and technology benefiting people special project(No.18-6-1-99-nsh)Open project of chemistry department of Qingdao university of science and technology(QUSTHX201930)
文摘In the process of liquid-liquid extraction,it is necessary to look for green solvents as extractants.Ionic liquids have been studied as extractants due to their green recyclability in recent years.The infinite dilution activity coefficients of 100 ionic liquids with a combination of 10 cations and 10 anions were calculated by COSMO-SAC model,and theσ-profiles were plotted.The distribution coefficient and separation coefficient of n-heptane+tert-butanol+ILs were determined.[OMIM][OTF],[HMIM][OTF]and[BMIM][OTF]were selected as solvents for this study.The interaction energy,bond length and charge density of ionic liquids with tert-butanol were calculated by quantum chemistry calculation method.According to these results,the rationality of selected ionic liquids as extractants could be analyzed from the molecular level.At 298.15 K and 101.325 kPa,the liquid-liquid equilibrium data of the ternary system{n-heptane+tert-butanol+[OMIM][OTF],nheptane+tert-butanol+[BMIM][OTF],n-heptane+tert-butanol+[HMIM][OTF]}were measured.The distribution coefficient and separation coefficient for judging the extraction effect were obtained.The NRTL model was used to correlate liquid-liquid equilibrium experimental data,and correlation result proved that the correlated and experimental data had a good correlation.The research on ionic liquids is of great significance to the development of green and sustainable chemical industry.
