Research advances of rare earth catalysts for catalytic purification of vehicle exhausts-Commemorating the 100th anniversary of the birth of Academician Guangxian Xu

Nowadays,air pollution has become a prominent environmental problem and has attracted much attention.With the increase of vehicle retention quantity,the exhaust emissions have become the main sources of air pollution.To reduce pollution and hazards,vehicle exhaust emission regulations are becoming stricter and stricter,which puts forward higher requirements for purification of vehicle exhausts.At present,rare earths have been widely applied in vehicle exhaust purification because of their good catalytic performance,which is attributed to their unique 4 f electron layer structure occupied without full electrons,excellent oxygen storage/release capacity and redox ability.In this paper,the current status of rare earth catalysts and application of rare earth in different fuel vehicle exhaust catalysts,including three-way catalysts(TWCs)for gasoline vehicles,diesel exhaust catalysts for different pollutants(particulate matter(PM),NOx,CO and HC)and catalysts for new energy vehicles with different fuels,are summarized in detail.Meanwhile,the corresponding mechanisms and the role of rare earth in vehicle exhaust catalysts are also simultaneously described.Furthermore,the challenges and development directions of rare earth catalysts for the purification of vehicle exhausts are also proposed.

One-step hydrothermal synthesis of Cu-SAPO-34/cordierite and its catalytic performance on NO_x removal from diesel vehicles

Cu-SAPO-34/cordierite catalysts were prepared via one-step hydrothermal synthesis method and their performances to remove NO x from the diesel vehicle exhaust were evaluated. The morphology, structure, Cu content and valence state were characterized by SEM, XRD, ICP and XPS, respectively. The experimental results show the active component Cu of the catalysts via in situ synthesis could significantly improve the selective catalytic reduction （SCR） activities of NOx and the optimal Cu content is in the range of 0.30%-0.40%（mass fraction）. No N 2 O is detected by gas chromatograph （GC） during the evaluation process, which implies that NOx is almost entirely converted to N2 over Cu-SAPO-34/cordierite catalyst. The conversion rate of NOx to N2 by NH3 over catalyst could almost be up to 100%in the temperature range of 300-670 ℃with a space velocity of 12000 h-1 and it is still more than 60% at 300-620 ℃ under 36000 h-1. The catalysts also show the good hydrothermal and chemical stability at the atmosphere with H 2 O.

CeO_2-ZrO_2-La_2O_3-Al_2O_3 composite oxide and its supported palladium catalyst for the treatment of exhaust of natural gas engined vehicles

Composite supports CeO2-ZrO2-Al2O3（CZA） and CeO2-ZrO2-Al2O3-La2O3（CZALa） were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles （NGVs） operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction （XRD） and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000 ℃. The results of N2-adsorption, H2-temperatnre-programmed reduction （H2-TPR） and oxygen storage capacity （OSC） measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.

Comparison of the Mutagenicity of Exhaust Emissions From Motor Vehicles Using Leaded and Unleaded Gasoline as Fuel

While Unleaded gasoline has the advantage of eliminating lead from automobile exhaust, its potential to reduce the exhaust gas and particles, merits further examination. In the present studies,the concentrations of hydrocarbons (HC) and earbon monoxides (CO) in emissions were analyzed on Santana engine Dynamometer under a standard test cycle, and total exhaust particles were collected from engines using leaded and unleaded gasoline. It was found that unleaded gasoline reduced the emissions of CO and HC, and decreased the quantity of vehicle exhaust particulate matters by 60%.With the unlead gasoline, only 23 kinds of organic substances, adsorbed in the particles, were identified by gas chromatography/mass spectrometer (GC/MS) while 32 components were detected using the leaded gasoline. The results of in vitro Salmonella/ microsomal test and micronucleus induction assay in CHL cells indicated that both types of gasoline increased the number of histidine-independent colonies and the frequencies of micronucleus induction; no significant differellce was found in their mutagenicity.

Study of Vehicle Exhaust Variation with Test Modes

Nowadays harmful gas in vehicle exhaust has pollute d air heavily. To prevent the environment from polluting, the request of emissions control legislation becomes more stringent. New legislation prescribes not only the emissions limitation of vehicles, but also testing instruments and methods. Test car must be operated on the chassis dynamometer and data must be collect ed and analyzed with prescriptive exhaust analysis system as well. The mass of harmful exhaust gas, containing the concentration and volume of emis sion, which is independent from the model of automobile and engine, can be used as a criterion to evaluate the pollution of an automobile. Constant Volume Sampl e System (CVS) is used to measure vehicle emissions, but it is too expensive to apply extensively. The Vehicle Mass Analysis System(Vmas), a new vehicle exhaust mass analysis system produced in USA late 1990s,is used to test and analyze veh icle exhaust. As a test instrument, it has the virtue of cheapness and easy mana geability. In this paper, Vmas is used to measure the emissions of a light truck CA1020F. A ccording to 15 running modes of Vehicle Exhaust Legislation, the test car is ope rated on the chassis dynamometer and data are collected and analyzed with Vmas. The test results show that it is viable to measure and evaluate automobile emiss ion with Vmas. Most of HC exhaust is produced when the car is decelerating. The major factor that influences the mass of HC emission is the sudden decrease of e ngine load causing incomplete combustion in decelerating mode. Test results indi cate CO and NOx are mainly produced in the process of increasing load. The forme r reason is incomplete combustion and the latter is high burning temperature cau sed by the increasing load. The methods of reducing automobile emission are also discussed in this paper.

Study on Influence of Gasoline Sulfur Content on Performance of Vehicle Exhaust Catalytic Converter

This paper has investigated the influence of gasoline sulfur content on durability of catalytic converter for vehicle exhaust gas. Two gasoline samples with different sulfur contents (equating to 150 μg/g and 50 μg/g of sulfur, respectively) were used to examine the durability and performance of catalytic converter on the bench test. The test results have revealed that in comparison to the influence of sulfur on ageing of catalytic converter the thermal ageing had a more remarkable impact on the performance of catalytic converter, and the performance of catalytic converter could be restored by high-temperature desulfurization process after ageing by the high-sulfur gasoline sample (containing 150 μg/g of sulfur) .

COMPOSITIVE EMISSION CONTROL SYSTEM OF GASOLINE VEHICLE

The working principle of a kind of compositive emission control system is inquired into, which includes exhaust heater, secondary air supplement, exhaust gas recirculation （EGR）, thermal reactor and catalytic converter, etc. The purification effect of CO, HC and NOx emission of the gasoline spark ignite （S.I.） engine is studied. The entire vehicle driving cycle tests based on the national emission standard and a series of the gasoline engine-testing bench tests including full load characteristic experiment, load characteristic experiment and idle speed experiment are done. The results show that the system has a very good emission control effect to CO, HC and NOx of gasoline engine. The construction of the system is very simple and can be mounted on the exhaust pipe conveniently without any alteration of the vehicle-use gasoline engine.

PAHs pollution from traffic sources in air of Hangzhou, China: Trend and influencing factors

PAHs pollution in air of arterial roads was investigated from October 1998 to October 2001 in Hangzhou, China. The results showed that Σ10 PAHs was 13—36 μg/m3, among which, BaP, a strong carcinogenic kind ranged from 0.034 μg/m3 to 0.12 μg/m3. PAHs pollutions in four seasons were winter>autumn>spring-summer. The annual averages of ΣPAHs concentration were 25 μg/m3 for 1999, 28 μg/m3 for 2000, and 29 μg/m3 for 2001, respectively. Leaded gasoline was banned in December 1998 in Hangzhou, thus comparative measurements with PAHs in leaded and lead-free gasoline powered motor exhausts made it certain that the use of lead-free gasoline leaded to a heavier PAHs pollution in roadside air from December, 1998, in China, and ΣPAHs in air samples after the lead-banning were more than twice of that in samples before the action. For the large contribution of vehicle discharge to air pollution in roadside, further research was performed to suggest the factors influencing PAHs distribution in vehicle exhaust in order to control air pollution effectively. Compared to gasoline engines, emissions from diesel engines were less toxic, although they might produce more PAHs. Of the same vehicular and oil type, automobiles of longer mileages produced more toxic PAHs. PAHs distributions in the vehicular exhausts were related to the oil type. Large difference was found in the abundance of 3-, 5- and 6-ring PAHs between exhausts from gasoline and diesel oil engines. Diesel oil engines produced relative lighter PAHs such as NAPH, ACEN, FLUOR, while gasoline engines emitted heavier kinds such as BkF, IN and BP. The automobile produced more PAHs with the increase of mileage especially FLUR, PY, BaP, BP. Some significant ratios for traffic source in Hangzhou such as PHEN/AN, FLUR/PY, IN/BP were 0.50—4.3, 0.58—7.4, 0.51—1.5, respectively. A source fingerprint for vehicle exhausts of a mixture of vehicle and oil types in the city district for light-duty vehicle was the abundance of BaA, followed by NAPH, BP, IN. 4-ring PAHs such as FLUR, PY, BaA and CHRY were the most predominant kinds followed by 6-ring PAHs(BP, IN).

Commuter exposure to BTEX in public transportation modes in Bangkok, Thailand

Measurements and monitoring of volatile organic compounds （VOCs） have been conducted in the metropolitan Bangkok. However, in-vehicle levels of VOCs are still lacking. This study investigated VOCs concentrations in four public transportation modes in Bangkok, Thailand during two rush hour periods （7：00–9：00 a.m. and 4：00–7：00 p.m.）. The four modes included an air-conditioned bus （A/C bus）, non-air-conditioned bus （non-A/C bus）, electric sky train, and a passenger boat traveling along the canal. Comparison among three important bus routes was also studied. In-vehicle air samples were collected using charcoal sorbent tubes and then analyzed by a gas chromatography-mass spectrometer. Results showed that the transportation modes significantly influenced the abundance of in-vehicle benzene, toluene, ethylbenzene, and m,p-xylene （BTEX）. Median concentrations of BTEX were 11.7, 103, 11.7, and 42.8 μg/m3 in A/C bus; 37.1, 174, 14.7, and 55.4 μg/m3 in non-A/C bus; 2.0, 36.9, 0.5, and 0.5 μg/m3 in sky train; and 3.1, 58.5, 0.5, and 6.2 μg/m3 in boat, respectively. Wilcoxon rank sum test indicated that toluene and m,p-xylene in the sky trains were statistically lower than that in the other three modes at a p-value of 0.05. There were statistical differences in TEX concentrations among the bus routes in the non-A/C buses. In addition, the benzene to toluene ratios implied that tail-pipe emissions were important contributor to the abundance of in-vehicle VOCs.

Effects of the Adjustment of Energy Structure on 24-h Average of NO_2 Concentration in Different Regions of Urumqi City in Winter

[ Objective] The study aimed to discuss the effects of the adjustment of energy structure on daily average concentration of NO2 in different regions of Urumqi city in winter. [ Method] The changes of daily average concentration of NO2 in different areas of Urumqi City from January to February （ NO2 pollution was most serious） before and after the implementation of the project ＂changing coal to gas＂ were analyzed. [ Result] After the implementation of the project, daily average concentration of NO2 in different areas of Urumqi City was increased due to the rapid increase of ve- hicle quantity, but there were certain differences in the increase among various regions. From south to north, daily average concentration of NO2 in winter was decreased gradually, that is, daily average concentration of NO2 was the highest in the south area, while in the north area, it didn＇t change significantly before and after the implementation of the project, but it was still high. Therefore, the local government should pay more attention to pollution NO2 during environmental management process. [ Conclusion] The research could provide scientific references for the control of atmospheric pollution in future.

Role of ammonia in forming secondary aerosols from gasoline vehicle exhaust

Ammonia(NH3) plays vital roles in new particle formation and atmospheric chemistry. Although previous studies have revealed that it also influences the formation of secondary organic aerosols(SOA) from ozonolysis of biogenic and anthropogenic volatile organic compounds(VOCs), the influence of NH3 on particle formation from complex mixtures such as vehicle exhausts is still poorly understood. Here we directly introduced gasoline vehicles exhausts(GVE) into a smog chamber with NH3 absorbed by denuders to examine the role of NH3 in particle formation from GVE. We found that removing NH3 from GVE would greatly suppress the formation and growth of particles. Adding NH3 into the reactor after 3 h photo-oxidation of GVE, the particle number concentration and mass concentrations jumped explosively to much higher levels, indicating that the numbers and mass of particles might be enhanced when aged vehicle exhausts are transported to rural areas and mixed with NH3-rich plumes. We also found that the presence of NH3 had no significant influence on SOA formation from GVE. Very similar oxygen to carbon(O:C) and hydrogen to carbon(H:C) ratios resolved by aerosol mass spectrometer with and without NH3 indicated that the presence of NH3 also had no impact on the average carbon oxidation state of SOA from GVE.

High impact of vehicle and solvent emission on the ambient volatile organic compounds in a major city of northwest China

Monitoring of ambient volatile organic compounds(VOCs)was conducted within typical residentialcommercial area in the city of Xi’an in northwest China during typical ozone(O_(3))episodes,to investigate the major contributors to the characteristic of ambient VOCs and their impact on O_(3) production.In the residential-commercial area,diurnal variation of VOCs was highly impacted by vehicle exhaust,fuel evaporation,and local solvent use.Relative higher contributions(up to 60%)of VOCs from solvent use to the ozone formation potential were found.The present findings highlight the urgent need for restrictions on the emission of VOCs from solvent use and non-vehicle-traffic-related sources,such as oil storage.

Seasonal variations of mass absorption efficiency of elemental carbon in PM_(2.5) in urban Guangzhou of South China

This study investigates seasonal variations of mass absorption efficiency of elemental carbon(MAE_(EC))and possible influencing factors in urban Guangzhou of South China.Mass concentrations of elemental carbon(EC)and organic carbon(OC)in PM_(2.5) and aerosol absorption coefficient(b_(ap))at multi-wavelengths were simultaneously measured in four seasons of 2018-2019 at hourly resolution by a semi-continuous carbon analyzer and an aethalometer.Seasonal average mass concentrations of EC were in the range of 1.36-1.70μgC/m^(3) with a lower value in summer than in the other seasons,while those of OC were in the range of 4.70–6.49μgC/m^(3) with the lowest value in summer and the highest in autumn.Vehicle exhaust from local traffic was identified to be the predominant source of carbonaceous aerosols.The average aerosol absorption Angstrom exponents(AAE)were lower than 1.2 in four seasons,indicating EC and b_(ap) were closely related with vehicle exhaust.Seasonal MAE EC at 550 nm was 11.0,8.5,10.4 and 11.3 m^(2)/g in spring,summer,autumn,and winter,respectively.High MAE EC was related with the high mass ratio of non-carbonaceous aerosols to EC and high ambient relative humidity.

Major reactive species of ambient volatile organic compounds (VOCs) and their sources in Beijing

Volatile organic compounds(VOCs)are important precursors of atmospheric chemical processes.As a whole mixture,the ambient VOCs show very strong chemical reactivity.Based on OH radical loss rates in the air,the chemical reactivity of VOCs in Beijing was calculated.The results revealed that alkenes,accounting for only about 15%in the mixing ratio of VOCs,provide nearly 75%of the reactivity of ambient VOCs and the C4 to C5 alkenes were the major reactive species among the alkenes.The study of emission characteristics of various VOCs sources indicated that these alkenes are mainly from vehicle exhaust and gasoline evaporation.The reduction of alkene species in these two sources will be effective in photochemical pollution control in Beijing.

On-Line Defect Detection of Aluminum Coating Using Fiber Optic Sensor

Aluminum metallization using the sprayed coating for exhaust mild steel （MS） pipes of tractors is a standard practice for avoiding rusting. Patches of thin metal coats are prone to rusting and are thus considered as defects in the surface coating. This paper reports a novel configuration of the fiber optic sensor for on-line checking the aluminum metaUization uniformity and hence for defect detection. An optimally chosen high bright 440 nm BLUE LED （light-emitting diode） launches light into a transmitting fiber inclined at the angle of 60° to the surface under inspection placed adequately. The reflected light is transported by a receiving fiber to a blue enhanced photo detector. The metallization thickness on the coated surface results in visually observable variation in the gray shades. The coated pipe is spirally inspected by a combination of linear and rotary motions. The sensor output is the signal conditioned and monitored with RISHUBH DAS. Experimental results show the good repeatability in the defect detection and coating non-uniformity measurement.