Carbonate reservoirs generally achieved relatively low primary resource recovery rates.It is therefore often necessary to clean those reservoirs up and/or stimulate them post drilling and later in their production lif...Carbonate reservoirs generally achieved relatively low primary resource recovery rates.It is therefore often necessary to clean those reservoirs up and/or stimulate them post drilling and later in their production life.A common and basic carbonate reservoir cleanup technique to remove contaminating material from the wellbore is acidizing.The efficiency of acid treatments is determined by many factors,including:the type and quantity of the acid used;the number of repeated treatments performed,heterogeneity of the reservoir,water cut of the reservoir fluids,and presence of idle zones and interlayers.Post-treatment production performance of such reservoirs frequently does not meet design expectations.There is therefore much scope to improve acidizing technologies and treatment designs to make them more reliable and effective.This review considers acid treatment technologies applied to carbonate reservoirs at the laboratory scale and in field-scale applications.The range of acid treatment techniques commonly applied are compared.Differences between specific acid treatments,such as foamed acids,acid emulsions,gelled and thickened acid systems,targeted acid treatments,and acid hydraulic fracturing are described in terms of the positive and negative influences they have on carbonate oil production rates and recovery.Opportunities to improve acid treatment techniques are identified,particularly those involving the deployment of nanoparticles(NPs).Due consideration is also given to the potential environmental impacts associated with carbonate reservoir acid treatment.Recommendations are made regarding the future research required to overcome the remaining challenges pertaining to acid treatment applications.展开更多
Acid production with flue gas is a complex nonlinear process with multiple variables and strong coupling.The operation data is an important basis for state monitoring,optimal control,and fault diagnosis.However,the op...Acid production with flue gas is a complex nonlinear process with multiple variables and strong coupling.The operation data is an important basis for state monitoring,optimal control,and fault diagnosis.However,the operating environment of acid production with flue gas is complex and there is much equipment.The data obtained by the detection equipment is seriously polluted and prone to abnormal phenomena such as data loss and outliers.Therefore,to solve the problem of abnormal data in the process of acid production with flue gas,a data cleaning method based on improved random forest is proposed.Firstly,an outlier data recognition model based on isolation forest is designed to identify and eliminate the outliers in the dataset.Secondly,an improved random forest regression model is established.Genetic algorithm is used to optimize the hyperparameters of the random forest regression model.Then the optimal parameter combination is found in the search space and the trend of data is predicted.Finally,the improved random forest data cleaning method is used to compensate for the missing data after eliminating abnormal data and the data cleaning is realized.Results show that the proposed method can accurately eliminate and compensate for the abnormal data in the process of acid production with flue gas.The method improves the accuracy of compensation for missing data.With the data after cleaning,a more accurate model can be established,which is significant to the subsequent temperature control.The conversion rate of SO_(2) can be further improved,thereby improving the yield of sulfuric acid and economic benefits.展开更多
Acid cleaning processes were performed on a class 100 laminar flow clean bench assembled inside a class 1000 clean room.The ultrapure water was produced by Millipore RO (Reverse Osmosis) and Milli-Q water purification...Acid cleaning processes were performed on a class 100 laminar flow clean bench assembled inside a class 1000 clean room.The ultrapure water was produced by Millipore RO (Reverse Osmosis) and Milli-Q water purification systems.The three purity grades of nitric acid used for cleaning include Merck reagent grade HNO3,Fisher 'TraceMetal' grade HNO3,and the purest Fisher 'Optima' grade HNO3.The various bottles,containers and other labware,which are in contact with the samples,are made of low-density polyethylene (LDPE) and FEP or PFA Teflon materials.The acid cleaning procedures of the bottles and other containers follow a successive four times cleaning through immersion in increasing purity of nitric acid baths at different concentrations during four weeks.The first acid bath is performed at room temperature,but the following three acid baths are heated on ceramic hotplates with a surface temperature of 45℃.In order to verify the efficiency of the acid cleaning method,cleaned bottles underwent a blank determination procedure using ELAN 6100 inductively coupled plasma spectrometry (ICP-MS).Results show that most measured trace elements are not detected and the elements detected are at very low concentrations.The blank values are comparable with that of bottles cleaned at Korea Polar Research Institute (KOPRI).Although the acid cleaning method is developed mainly for reliable measurements of trace elements in snow and ice samples,it can also be used for investigations of trace elements in other environmental samples.展开更多
The authors discovered a new way to clean the ion exchange resin sorption of uranium from silicic acid used solution ＂Ayanat＂. The method reduces the costs of regeneration of ion exchange resin and its reuse in the ...The authors discovered a new way to clean the ion exchange resin sorption of uranium from silicic acid used solution ＂Ayanat＂. The method reduces the costs of regeneration of ion exchange resin and its reuse in the sorption of uranium.展开更多
Viscoelastic surfactants(VES)are often used as viscous diverters in acidizing stimulation to prolong the acid consumption time and maximize zonal coverage of the acid for improving well productivity.However,the ceilin...Viscoelastic surfactants(VES)are often used as viscous diverters in acidizing stimulation to prolong the acid consumption time and maximize zonal coverage of the acid for improving well productivity.However,the ceiling temperature of commercial VES cannot exceed 120℃in practical use because of the poor thermal stability and fragile molecular structure,hindering their implementation in hightemperature oil reservoirs,i.e.,≥150℃.Here we synthesized a novel C22-tailed diamine,N-erucaminopropyl-N,N-dimethylamine(EDPA),and examined comparatively its rheological behavior,assemblies morphology and molecular stability in 20 wt%HCl with a commercial VES,erucyl dimethyl amidopropyl betaine(EDAB).The feasibility of EDPA for acidizing stimulation was assessed by acid etching of carbonate rock with its HCl solution at 150℃.Rheological results showed that the 2.5 wt%EDPA—20 wt%HCl solution maintains stable viscosity of 90 m Pa s at 150℃for 60 min,while that of 2.0 wt%EDAB HCl solution is just 1 m Pa s under identical conditions.1H NMR spectra and cryo-TEM observations revealed that the chemical structure and self-assembled architectures of EDPA remained intact in such context,but the EDAB suffered from degradation due to the hydrolysis of the amide group,accounting for the poor heat-resistance and acid-tolerance.The reaction rate of 2.5 wt%EDPA HCl solution with carbonate rock was one order of magnitude lower than that of 20 wt%HCl solution at 150℃,underpinning the potential of EDPA to be used in the high-temperature reservoirs acidizing.This work improved the thermal tolerance of VES in highly concentrated HCl solution,paving a feasible way for the acidization of high-temperature reservoir environments(~150℃).展开更多
The textural features and acidic properties of sulfated mesoporous lanthana‐zirconia solid acids （SO42？/meso‐La0.1Zr0.9Oδ） were efficiently tuned by modifying the conditions used to prepare the meso‐La0.1Zr0.9O...The textural features and acidic properties of sulfated mesoporous lanthana‐zirconia solid acids （SO42？/meso‐La0.1Zr0.9Oδ） were efficiently tuned by modifying the conditions used to prepare the meso‐La0.1Zr0.9Oδcomposites, such as the molar ratio of the template to La and Zr metal ions （Nt/m）, molar ratio of ammonia to La and Zr metal ions （Na/m）, hydrothermal temperature （Thydro）, and hy‐drothermal time （thydro）. The effect of the textural features and acidic properties on the catalytic performance of solid acid catalysts for alkenylation of p‐xylene with phenylacetylene was investi‐gated. Various characterization techniques such as N2 physisorption, X‐ray diffraction, NH3 temper‐ature‐programmed desorption, and thermogravimetric analysis were employed to reveal the rela‐tionship between the nature of catalyst and its catalytic performance. It was found that the catalytic performance significantly depended on the textural features and acidic properties, which were strongly affected by preparation conditions of the meso‐La0.1Zr0.9Oδcomposite. Appropriate acidic sites and high accessibility were required to obtain satisfactory catalytic reactions for this reaction. It was also found that the average crystallite size of t‐ZrO2 affected by the preparation conditions had significant influence on the ultrastrong acidic sites of the catalysts. The optimized SO42？/meso‐La0.1Zr0.9Oδcatalyst exhibited much superior catalytic activity and coke‐resistant stabil‐ity. Moreover, the developed SO42？/meso‐La0.1Zr0.9Oδcatalyst demonstrated excellent catalytic per‐formance for alkenylation of diverse aromatics with phenylacetylene to their correspondingα‐arylstyrenes. Combining the previously established complete regeneration of used catalysts by a facile calcination process with the improved catalytic properties, the developed SO42？/meso‐La0.1Zr0.9Oδ solid acid could be a potential catalyst for industrial production ofα‐arylstyrenes through clean and atom efficient solid‐acid‐mediated Friedel‐Crafts alkenylation of diverse aromatics with phenylacetylene.展开更多
12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions u...12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide（H2O2） as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds（S-compounds） molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene（DBT） and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.展开更多
Industrial production process including nitric acid production is an important greenhouse gas emission source. Although IPCC guidelines have given calculation methods and emission factors for N2O emission from nitric ...Industrial production process including nitric acid production is an important greenhouse gas emission source. Although IPCC guidelines have given calculation methods and emission factors for N2O emission from nitric acid production, emission factors of nitric acid production in China are not given. And it can be seen from the comparison of the guidelines and registered CDM projects in China that the N2O emission factors given in the IPCC guidelines and actual N2O emission from nitric acid production in China differ greatly while measured N2O emission data is not available, so determination of emission factors for N2O emission from nitric acid production is an important basic research for N2O emission calculation in China. The method that calculate N2O emission factors from nitric acid production in China is studied with baseline emission factors based on actual measurement of registered CDM projects and the calculated emission factor is compared with that given in the IPCC guidelines in the text.展开更多
基金supported by the Tomsk Polytechnic University development program.
文摘Carbonate reservoirs generally achieved relatively low primary resource recovery rates.It is therefore often necessary to clean those reservoirs up and/or stimulate them post drilling and later in their production life.A common and basic carbonate reservoir cleanup technique to remove contaminating material from the wellbore is acidizing.The efficiency of acid treatments is determined by many factors,including:the type and quantity of the acid used;the number of repeated treatments performed,heterogeneity of the reservoir,water cut of the reservoir fluids,and presence of idle zones and interlayers.Post-treatment production performance of such reservoirs frequently does not meet design expectations.There is therefore much scope to improve acidizing technologies and treatment designs to make them more reliable and effective.This review considers acid treatment technologies applied to carbonate reservoirs at the laboratory scale and in field-scale applications.The range of acid treatment techniques commonly applied are compared.Differences between specific acid treatments,such as foamed acids,acid emulsions,gelled and thickened acid systems,targeted acid treatments,and acid hydraulic fracturing are described in terms of the positive and negative influences they have on carbonate oil production rates and recovery.Opportunities to improve acid treatment techniques are identified,particularly those involving the deployment of nanoparticles(NPs).Due consideration is also given to the potential environmental impacts associated with carbonate reservoir acid treatment.Recommendations are made regarding the future research required to overcome the remaining challenges pertaining to acid treatment applications.
基金supported by the National Natural Science Foundation of China(61873006)Beijing Natural Science Foundation(4204087,4212040).
文摘Acid production with flue gas is a complex nonlinear process with multiple variables and strong coupling.The operation data is an important basis for state monitoring,optimal control,and fault diagnosis.However,the operating environment of acid production with flue gas is complex and there is much equipment.The data obtained by the detection equipment is seriously polluted and prone to abnormal phenomena such as data loss and outliers.Therefore,to solve the problem of abnormal data in the process of acid production with flue gas,a data cleaning method based on improved random forest is proposed.Firstly,an outlier data recognition model based on isolation forest is designed to identify and eliminate the outliers in the dataset.Secondly,an improved random forest regression model is established.Genetic algorithm is used to optimize the hyperparameters of the random forest regression model.Then the optimal parameter combination is found in the search space and the trend of data is predicted.Finally,the improved random forest data cleaning method is used to compensate for the missing data after eliminating abnormal data and the data cleaning is realized.Results show that the proposed method can accurately eliminate and compensate for the abnormal data in the process of acid production with flue gas.The method improves the accuracy of compensation for missing data.With the data after cleaning,a more accurate model can be established,which is significant to the subsequent temperature control.The conversion rate of SO_(2) can be further improved,thereby improving the yield of sulfuric acid and economic benefits.
基金supported by National Natural Sciences Funds for Distinguished Young Scholar (40825017)the Chinese Academy of Sciences (SKLCS-ZZ-2008-06)
文摘Acid cleaning processes were performed on a class 100 laminar flow clean bench assembled inside a class 1000 clean room.The ultrapure water was produced by Millipore RO (Reverse Osmosis) and Milli-Q water purification systems.The three purity grades of nitric acid used for cleaning include Merck reagent grade HNO3,Fisher 'TraceMetal' grade HNO3,and the purest Fisher 'Optima' grade HNO3.The various bottles,containers and other labware,which are in contact with the samples,are made of low-density polyethylene (LDPE) and FEP or PFA Teflon materials.The acid cleaning procedures of the bottles and other containers follow a successive four times cleaning through immersion in increasing purity of nitric acid baths at different concentrations during four weeks.The first acid bath is performed at room temperature,but the following three acid baths are heated on ceramic hotplates with a surface temperature of 45℃.In order to verify the efficiency of the acid cleaning method,cleaned bottles underwent a blank determination procedure using ELAN 6100 inductively coupled plasma spectrometry (ICP-MS).Results show that most measured trace elements are not detected and the elements detected are at very low concentrations.The blank values are comparable with that of bottles cleaned at Korea Polar Research Institute (KOPRI).Although the acid cleaning method is developed mainly for reliable measurements of trace elements in snow and ice samples,it can also be used for investigations of trace elements in other environmental samples.
文摘The authors discovered a new way to clean the ion exchange resin sorption of uranium from silicic acid used solution ＂Ayanat＂. The method reduces the costs of regeneration of ion exchange resin and its reuse in the sorption of uranium.
基金the financial support from the National Natural Science Foundation of China(Nos:21773161,22172108)。
文摘Viscoelastic surfactants(VES)are often used as viscous diverters in acidizing stimulation to prolong the acid consumption time and maximize zonal coverage of the acid for improving well productivity.However,the ceiling temperature of commercial VES cannot exceed 120℃in practical use because of the poor thermal stability and fragile molecular structure,hindering their implementation in hightemperature oil reservoirs,i.e.,≥150℃.Here we synthesized a novel C22-tailed diamine,N-erucaminopropyl-N,N-dimethylamine(EDPA),and examined comparatively its rheological behavior,assemblies morphology and molecular stability in 20 wt%HCl with a commercial VES,erucyl dimethyl amidopropyl betaine(EDAB).The feasibility of EDPA for acidizing stimulation was assessed by acid etching of carbonate rock with its HCl solution at 150℃.Rheological results showed that the 2.5 wt%EDPA—20 wt%HCl solution maintains stable viscosity of 90 m Pa s at 150℃for 60 min,while that of 2.0 wt%EDAB HCl solution is just 1 m Pa s under identical conditions.1H NMR spectra and cryo-TEM observations revealed that the chemical structure and self-assembled architectures of EDPA remained intact in such context,but the EDAB suffered from degradation due to the hydrolysis of the amide group,accounting for the poor heat-resistance and acid-tolerance.The reaction rate of 2.5 wt%EDPA HCl solution with carbonate rock was one order of magnitude lower than that of 20 wt%HCl solution at 150℃,underpinning the potential of EDPA to be used in the high-temperature reservoirs acidizing.This work improved the thermal tolerance of VES in highly concentrated HCl solution,paving a feasible way for the acidization of high-temperature reservoir environments(~150℃).
基金financially supported by the National Natural Science Foundation of China (21276041)the Program for New Century Excellent Talents in University of Ministry of Education (NCET-12-0079)+1 种基金the Natural Science Foundation of Liaoning Province (2015020200)the Fundamental Research Funds for the Central Universities (DUT15LK41)~~
文摘The textural features and acidic properties of sulfated mesoporous lanthana‐zirconia solid acids （SO42？/meso‐La0.1Zr0.9Oδ） were efficiently tuned by modifying the conditions used to prepare the meso‐La0.1Zr0.9Oδcomposites, such as the molar ratio of the template to La and Zr metal ions （Nt/m）, molar ratio of ammonia to La and Zr metal ions （Na/m）, hydrothermal temperature （Thydro）, and hy‐drothermal time （thydro）. The effect of the textural features and acidic properties on the catalytic performance of solid acid catalysts for alkenylation of p‐xylene with phenylacetylene was investi‐gated. Various characterization techniques such as N2 physisorption, X‐ray diffraction, NH3 temper‐ature‐programmed desorption, and thermogravimetric analysis were employed to reveal the rela‐tionship between the nature of catalyst and its catalytic performance. It was found that the catalytic performance significantly depended on the textural features and acidic properties, which were strongly affected by preparation conditions of the meso‐La0.1Zr0.9Oδcomposite. Appropriate acidic sites and high accessibility were required to obtain satisfactory catalytic reactions for this reaction. It was also found that the average crystallite size of t‐ZrO2 affected by the preparation conditions had significant influence on the ultrastrong acidic sites of the catalysts. The optimized SO42？/meso‐La0.1Zr0.9Oδcatalyst exhibited much superior catalytic activity and coke‐resistant stabil‐ity. Moreover, the developed SO42？/meso‐La0.1Zr0.9Oδcatalyst demonstrated excellent catalytic per‐formance for alkenylation of diverse aromatics with phenylacetylene to their correspondingα‐arylstyrenes. Combining the previously established complete regeneration of used catalysts by a facile calcination process with the improved catalytic properties, the developed SO42？/meso‐La0.1Zr0.9Oδ solid acid could be a potential catalyst for industrial production ofα‐arylstyrenes through clean and atom efficient solid‐acid‐mediated Friedel‐Crafts alkenylation of diverse aromatics with phenylacetylene.
基金Razi University Research Council for support of this work
文摘12-Tungstophosphoric acid（PW） supported on KSF montmorillonite, PW/KSF, was used as catalyst for deep oxidative desulfurization（ODS） of mixed thiophenic compounds in model oil and crude oil under mild conditions using hydrogen peroxide（H2O2） as an oxidizing agent. A one-factor-at-a-time method was applied for optimizing the parameters such as temperature, reaction time, amount of catalyst, type of extractant and oxidant-tosulfur compounds（S-compounds） molar ratio. The corresponding products can be easily removed from the model oil by using ethanol as the best extractant. The results showed high catalytic activity of PW/KSF in the oxidative removal of dibenzothiophene（DBT） and mixed thiophenic model oil under atmospheric pressure at 75 ℃ in a biphasic system. To investigate the oxidation and adsorption effects of crude oil composition on ODS, the effects of cyclohexene, 1,7-octadiene and o-xylene with different concentrations were studied.
文摘Industrial production process including nitric acid production is an important greenhouse gas emission source. Although IPCC guidelines have given calculation methods and emission factors for N2O emission from nitric acid production, emission factors of nitric acid production in China are not given. And it can be seen from the comparison of the guidelines and registered CDM projects in China that the N2O emission factors given in the IPCC guidelines and actual N2O emission from nitric acid production in China differ greatly while measured N2O emission data is not available, so determination of emission factors for N2O emission from nitric acid production is an important basic research for N2O emission calculation in China. The method that calculate N2O emission factors from nitric acid production in China is studied with baseline emission factors based on actual measurement of registered CDM projects and the calculated emission factor is compared with that given in the IPCC guidelines in the text.
