• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 法律状态
  • 优先权
    • 专利摘要:
    An improved nanoparticle counter having a gas treatment stage prior to a nanoparticle counter, said gas treatment stage comprising an oxidation catalyst and an absorber effective in absorbing gaseous sulfur compounds and, desirably, nitrogen oxides which, when cooled, nucleate and form particles, the gas treatment step one or more flow monoliths are applied, the gas treatment step being applied to a metal foil monolith of not more than 400 cells / inch 2 and a film thickness of not more than 50 microns and having an open area of at least 90%.
    公开号:AT516654A2
    申请号:T9388/2014
    申请日:2014-10-06
    公开日:2016-07-15
    发明作者:
    申请人:Twigg Scient & Technical Ltd；
    IPC主号:
    专利说明:

    IMPROVEMENTS IN NANOPARTICLE COUNTING
    The present invention relates to improvements in nanoparticle counting and, more particularly, relates to the counting of solid particles in an atmosphere containing condensable hydrocarbons and sulfate-type species.
    For environmental and health reasons, it has become important to count the number of nanoparticles (size less than 100 nm) in a gaseous atmosphere. In particular, internal combustion engines emit particulates beyond regulated gaseous pollutants such as NOx, CO, partially burned and unburned hydrocarbons (HC). While large carbonaceous particulates evolved the highly visible diesel "smoke" expelled by older design diesel engines, and especially when the engine was under load, modern turbo charged, high temperature charged air cooled diesel engines continue to emit less visible, smaller particulates , In addition, gasoline engines, especially those of gasoline direct injection design, eject large numbers of small particles. The regulations known as EURO 5 Reg 83 apply to exhaust gas flows from vehicle diesel engines.
    Nanoparticles in IC engine exhaust can not easily be counted using technology such as laser light scattering instruments, which, however, can be used for larger micron-sized particles. Known as condensation particle counter ("CPC") instruments are commercially available in which the particle-containing gas is passed through a supersaturated vapor, conventionally a vapor of an organic liquid such as isopropanol or n-butanol, though steam has been used, so that the Particles act as nuclei for the vapor condensation. Accordingly, under appropriate conditions, the nanoparticles can grow to sizes of up to 10-12 pm and thus can be counted using conventional flare technology. A problem with this system, however, is that any type of particle can act as a nucleus, not just solid carbonaceous or metal oxide particles. This problem is exacerbated by the high dilutions used in the counting technique. IC engine exhaust gases include, beyond the solid carbonaceous or metal oxide particles of legal interest, hydrocarbons and other organic condensed solids and sulfur compounds, and may include nitrogen oxides, organic acids, and phosphoric acids. Each of these components may, under some circumstances, act as a core and, correspondingly, obscure the counting process. Some efforts have been made by adjusting the conditions in the CPC and by signal processing to distinguish between true solid particles and pseudo-solid cores, but there is a continuing need for alternative approaches, especially as increasing attention is paid to the potential hazards of nanoparticle emissions. SAE paper no. 950236 from 1995 suggests measuring volatile and solid exhaust particulates. The equipment described uses a catalytic stripper, which is an area of a diesel exhaust catalyst; a diluted exhaust stream is passed through the diesel exhaust catalyst before it is cooled and sent to a particle counter, such as a diesel engine. an electrical aerosol analyzer or a condensation core counter (CNC). An alternating stream of dilute gas is passed to the particle counter with the omission of the catalytic stripper treatment to allow determination of total, volatile and non-volatile (solid) particle concentrations. This device is also described in US patent application US 2004/0139785.
    However, the catalytic stripping concept appears to have been abandoned and the European regulations only require the treatment of the exhaust gas in a heated tube to trap all volatile components in the vapor phase, and air dilution and cooling to prevent nucleation before passing the catalyst To avoid exhaust gas to a CNC for particle counting.
    Prof. Nick Collings has recently investigated a high-temperature condensation particle counter that avoids the problem of condensation or nucleation of volatile material during particle measurement in exhaust gases. See www.cambridqeparticlemeetinq.org/sites/default/files/Presentations/2013/NCollinqs(UofCambridge) 2013 Hotcondensationparticlecounter.pdf
    The inventor of the present invention has attempted to solve the problem of analyzing particulate matter by applying several alternative treatments to an exhaust gas, then passing the treated gas to a particle counter as described in WO 2004/097400 A1, and comparing and verifying the various results , One of the treatments involved contacting the gas sample with an oxidation catalyst to oxidize the hydrocarbons and a basic material to absorb acidic species. The preferred catalyst is alumina-applied platinum. The catalyst and absorber are suitably carried by a ceramic flow monolith. It is not believed that the described apparatus has ever found commercial use in any form. We have now developed a new and improved device as described below.
    However, there remains a need for a reliable particle counter that can handle the many different components in exhaust streams that can condense or nucleate, directly or indirectly by reaction with other components, and form particles that obscure a CPC or other particle counting instrument. In particular, it would be useful to construct a system that would be mountable in transportable instruments, such as e.g. Roadside test equipment or on-board test equipment, and it is believed that the present invention offers such a solution.
    The present invention now provides an improved nanoparticle counting instrument having a gas treatment stage prior to a nanoparticle counter, the gas treatment stage comprising an oxidation catalyst and an absorber which comprises absorbing gaseous sulfur compounds, desirably nitrogen oxides and other acidic vapor species which, when cooled, nucleation and particle formation, the gas treatment step being on a metal flow monolith having no more than 400 cells / inch 2 and having an open area of not less than 80%, preferably not less than 90%, and most desirably not less than 95% %, is applied. Preferably, the gas treatment step is contained in a replaceable unit, which may be disposed of after a predetermined period of use, for example. Alternatively, the unit may be recycled and / or regenerated.
    Although the present invention has been developed primarily with a conventional commercial CPC device, the principles can be applied to any particle counter that is subject to interference from non-solid "particles", particularly those derived from combustion gas streams. The present invention may desirably be combined with a high temperature condensation particle counter which obviates the need for cooling the gas stream leaving the absorber unit of the catalyst and associated potential particle diffusion losses.
    The gas treatment unit is conveniently but not principally contained within a single housing. Desirably, the housing is asymmetrical so that it can be mounted in conjunction with fittings only in the correct manner, that is, with the upstream catalyst zone. Conventional catalyst structures, such as those using a ceramic or metallic honeycomb-like flow-through substrate structure, can be used in the present invention. Structures prone to obstructing the flow of particles are not preferred because they can falsify particle count results. We believe that a key factor in avoiding particle flow obstruction is the open area of the monolith. For example, the prior art conventional ceramic monolith, as used in WO 2004/0907400-A, had a wall thickness of 8 mils (one-thousandth of an inch). We calculated that for a 400 cell per square inch monolith this would give an open area of 70.56%. SAE Paper No. 950236 uses a catalyst which is a ceramic
    Uses monoliths with a wall thickness of 12.2 mils; this would give an open area of 60.8%.
    The catalyst may be any catalytically active substance that is effective under the operating conditions. Suitably, the catalyst consists of or comprises a platinum group metal, preferably platinum or palladium, more preferably a palladium / platinum catalyst, although other materials, such as manganese, or other suitable metal compounds active therein under the particular conditions, Substantially all of the organic vapors and particularly hydrocarbons in the gas passed through the catalyst can be used. It is not desirable to oxidize SO 2 to sulfate species. The extent to which this happens depends on the catalyst formulation and the operating temperature. When operating at temperatures around 300-350 ° C, the amount of SO 2 oxidation should be low. Any SO 2 that is oxidized is absorbed at the absorber. It is not believed that S02 itself causes any significant impediment to particle counting.
    The catalyst may comprise a single component or may comprise one or more promoters or other active or inert components, including materials which increase the effective surface area of the catalyst or inhibit the oxidation of SO 2 to sulfate species.
    We have found that the application of the active catalytic oxidation phase, e.g. Platinum, on a washcoat comprising silica instead of the conventional and prior art clay, results in a desired resistance to catalyst poisoning by sulfur components. On top of that, it leads to prolonged high performance and catalyst life.
    Such catalysts may be fabricated according to our procedures by those skilled in the art.
    Positioned downstream of the catalyst is an absorber. Suitable absorbers include alkaline earth or alkali metal compounds, such as carbonates or oxides of barium, strontium or calcium, or similar materials effective in binding sulfate-type species. While the catalyst and absorber functions may be performed by separate units mounted within a housing through which the test gas is passed, it is also desirable in another embodiment, for the purpose of minimizing particulate loss, to be catalyst and catalyst Depositing absorber layers in sequence on the same carrier. Thus, a layer of an absorber-containing component may first be deposited on a catalyst support, for example, by spraying the catalyst support with or immersing the catalyst support in one
    Slurry or solution containing the absorber component or a precursor of the absorber component. Other catalyst coating operations, including vacuum coating, may be used. The thus-coated carrier may then be dried and calcined, after which the process is repeated with a slurry or solution containing catalyst components, optionally by inverting the carrier. In the case of a carrier monolith, this may thus yield a monolith coated upstream with a catalyst coating and downstream with an absorber coating. Other constructions of the unit will be apparent to those skilled in the art, and zones containing mixtures of catalyst and absorber or an inner layer of oxidation catalyst and an outermost layer of absorber may be advantageous.
    Desirably, the total unit of catalyst zone and absorber has a penetration of at least 80% for 10 nm particles (where penetration for a given particle size and specified conditions is 100 times the concentration of particles leaving the unit divided by the concentration of Particles defined entering the unit), more desirably a penetration of at least 90%. Accordingly, the use of flow through monoliths of relatively low cell density (not more than 400 cells per square inch) having a large open end area as specified above is preferred. In general, the use of shorter catalyst zones is preferred to minimize particle diffusion losses, provided that the zone is sufficient to achieve the desired level of catalytic oxidation. It should be noted that in WO 2004/0907400 mentioned above, the disclosure provided therein relates to a considerably different monolithic form, namely a diameter of 34 mm by a length of 110 mm.
    A novel monolith particularly suitable for use in the present invention is a metal foil monolith wherein the film has a maximum thickness of 50 microns, preferably 20 microns, and an open end area of at least 90%. The clear trend in catalyst technology is an increase in cell density in support monoliths; the present invention runs in the opposite direction to this tendency, at a maximum of 400 cells per square inch, and preferably not more than 200 cpsi.
    The sample gas and catalyst / absorber units are both preferably equipped with heaters to ensure that the catalyst is operated at the most advantageous temperature for the catalytic reactions and to ensure that all of the volatile material is in the vapor phase. This is generally in the range of 150 to 550 ° C, preferably in the range of 200 to 375 ° C. Those skilled in the art will recognize that the sample gas must be preheated to the desired operating temperature before it reaches the monolith, since achieving sufficient heat through a monolith, particularly a ceramic monolith, is virtually impossible.
    It will be appreciated that, depending on the concentration of non-solid particles in the test gas and the application the instrument experiences, the absorber will eventually be saturated (although desirably designed for extended operating time) and the catalyst itself Poisoning and coking can be less effective and the absorber can be saturated. It is therefore preferable to replace the catalyst / absorber unit before the unit becomes ineffective. Therefore, the unit is desirably in the form of an easily replaceable unit mounted in the particle counting instrument. While it is possible to consider regeneration of both catalyst and absorber, it is presently preferred to safely dispose of the unit. As mentioned above, the use of an asymmetrical design is preferred.
    In several of the tests on which this invention is based, a catalyst / absorber unit was about 42 mm long and was 19.05 mm in diameter (outside dimensions); a number of alternatives have also been used, for example, 38 mm in length and 22.2 mm in diameter with catalyst lengths of 37 mm and 32 mm, respectively. Active oxidation catalyst and absorber coatings within these units can range from 5 g / cubic foot to 200 g / cubic foot, and preferably 10 to 100 g / cubic foot, if the oxidation catalyst is a noble metal such as Pt, Pd, Rh and / or Au, and higher when derivatives of a base metal are used, such as Manganese oxides, and 20 g / cubic foot to 1000 g / cubic foot or more and preferably 50 g / cubic foot to 300 g / cubic foot for the absorber material.
    The invention will now be described by way of example. It should be noted that the specification of British units of measure, and not Sl or metric units, is customary for certain measurements in this field.
    Production of the gas treatment stage
    A cylindrical cordierite monolith having a plurality of square parallel channels (400 per square inch) running its length (6 inches), 5.66 inches in diameter, was immersed in an aqueous dispersion (35% by weight). ) of a high surface area dispersible silica / alumina comprising 30% silica and having a BET surface area of 140 m2 / g. The nominal wall thickness was 2.5 mils (thousandths of an inch) and we calculated that it had an open area of 90.2%. The dispersion was prepared by ball-milling the silica / alumina with water acidified to about pH = 4 with dilute nitric acid. Ball milling was continued until particle size (d50) ranged from 5-15 microns, as measured using a Malvern Instruments Mastersizer 2000. A small amount of dilute ammonia solution was then added gradually with stirring to gel the dispersion to the extent judged suitable for coating the monolith.
    The monolith was dipped in the dispersion, taken out therefrom, and drained for a few minutes. Excess dispersion was removed from the monolith by shaking and then blowing a stream of high velocity air from an air gun through the channels. The monolith was then dried by passing a stream of hot air (120 ° C) through the channels for a period of 3 hours, after which it was fired in static air in an electric furnace based on raising the temperature from ambient to 500 ° G for 2 hours, then holding this temperature for 2.5 hours, then allowed to cool to room temperature without applying heating. A comparison of the weight of the uncoated monolith with that of the monolith after coating and calcination revealed a washcoat layer of 2.3 grams per cubic inch of the gross volume of the monolith.
    Using a band saw, the washcoat-coated monolith was cut across its diameter into slices each 38 mm thick. The disks were impregnated by immersion in a solution to a depth of 25 mm in a shallow dish; additional solution was added to maintain the liquid depth as the solution was absorbed by the washcoat-coated monolith. The solution contained sufficient tetrammine platinum dinitrate such that in the dried and calcined state, the impregnated monolith contained 90 g Pt per cubic foot of the coated monolith. The impregnated solution also contained a small amount of ethylhydroxycellulose (Natrosol ™ Ashland Chemicals) to increase the viscosity of the solution sufficiently to prevent the solution from soaking on the monolith substantially above the level of the liquid in the dish. The appropriate concentration of the impregnating solution was determined by estimating the pore volume of the washcoat coated monolith by the cold water picking method. After impregnation, the partially platinized monolith was dried at 120 ° C for two hours and then calcined at 500 ° C for three hours as described above. After cooling, the partially platinized monolith was inverted and immersed in a 12.5 mm deep barium acetate solution in a dish. Again, the viscosity of the solution was controlled using Natrosol ™. As before, barium acetate solution was added to maintain the depth when solution was absorbed. After resting in the solution for several minutes, the monolith was carefully removed and drained on a raised wire mesh. The monolith was then dried at 120 ° C and calcined at 500 ° C as previously described. The coating with barium corresponded to 250 g Ba per cubic foot of the monolith. The resulting monolith had two zones along the length of the channels, one platinized 25 mm in length and one with barium 12.5 mm in length.
    The above procedure was repeated with a 350 cpsi metal foil monolith. Metal foil monoliths can generally be made with thinner wall areas than ceramic monoliths, which we find advantageous. A 25.3 mm long and 17.9 mm diameter outer stainless steel tube with 1 mm wall thickness was provided with an internal structure of 350 cells per square inch and made of a commercial catalyst monolith metal foil 0.05 mm thick. This is calculated as having an open area of 91.5%. The unit was cleaned with rinse-containing water, then rinsed several times with deionized water before being treated with pure acetone and air-dried. It was then heated in an electric furnace in an air atmosphere of 550 ° C for 3 hours to develop a thin resistant oxide film on the film surface. The unit was then coated three times using the procedure described above with a washcoat dispersion containing 19.5% solids as measured after drying and calcinations at 500 ° C. The final washcoat coating was equivalent to 2.0 grams per cubic inch of the total volume of the unit. The resulting washcoat-coated unit was then platinized along its entire length, corresponding to a coating of 90 grams per cubic foot. An outlet zone of 7.5 mm in length was impregnated with strontium acetate to contain 300 grams per cubic foot of strontium after calcination at 500 ° C for two hours.
    The washcoat-coated and zone-impregnated ceramic monolith was then cored using a diamond core drill to produce monoliths of 38 mm in length and about 16 mm in diameter. The cores were then stored in stainless steel (Type 316) jackets of suitable length (42 mm) and diameter (19 mm) and held in place by a swelling mat, followed by a heat treatment at 450 ° C in air for 3 hours in 300 Liters per hour of flowing air. Stainless steel inlet and outlet cones with 10 mm diameter central tube openings were welded to each unit for subsequent testing. Further units were made with different dimensions, e.g. Outside diameters of 22.2 mm and 25.4 mm and lengths of 35.5 mm and 31.0 mm, made.
    TESTS 1. Elimination of hydrocarbons
    In these tests, a unit described above (e.g., OD 19 mm, length 42 mm, not the monolith size) was configured so that the sample gas flow was first passed over the
    Oxidation part and then passed over the sulfur absorption part. Standard analytical and particle measurement techniques were used, and in all cases HEPA filtered air was considered to be a source of the gas in which hydrocarbon was vaporized using known amounts of the hydrocarbon of interest. The concentrations were checked by chromatographic analysis (FID). The hydrocarbon-containing gas was preheated to 350 ° C and the unit was maintained at the same temperature by means of an electric heater and a controller. The effluent gas was diluted with heated FIEPA filtered air prior to analysis. The condensable hydrocarbons used included decane, hexadecane and toluene. Gas flow rates through the unit ranged from 50 liters per hour to 500 liters per hour, and typically 180 liters per hour. The inlet concentrations of hydrocarbon were varied between 30 ppm and 1000 ppm, and within the experimental error, no hydrocarbon was detected in the exit gas, corresponding to at least 99.8% hydrocarbon removal. Tetracontain (C40H32), a "standard" volatile particulate in vehicle measurements, was vaporized before entering the unit. Particles in cooled gas were measured using standard commercial CPC procedures. With the unit held at room temperature, the expected number of particles was detected, and as the temperature was raised, the measured number decreased to effectively zero at 350 ° C. 2. Particle drenching
    Small particle penetration was measured to assess particle loss primarily through thermophoretic and diffusion processes in a unit equipped with short stainless steel cones and short 10 mm inlet and outlet tubes (as described above). Diesel engine exhaust-derived particles of known size were passed through the unit at room temperature (to minimize catalytic oxidation). Here, the penetration of 10 nm particles was greater than 80%. Similar results were obtained when metal particles were used at higher temperatures where hydrocarbons would be oxidized. The measured penetration depended on unit dimensions, flow rates and temperature. 3. Sulfur tolerance
    The unit's extraordinary tolerance to sulfur poisoning was demonstrated using test gas containing varying amounts of sulfur dioxide with hydrocarbon and air under the operating conditions described above over extended periods of time. In one experiment using n-decane, the unit with gas containing about 100 ppm of sulfur dioxide became 1000
    Hours were treated and there was no hydrocarbon detected in the exit gas stream as detected by gas chromatography. Particulate measurements on the exit gas did not detect particles resulting from nucleation of sulfuric acid, whereas a separate test with a conventional platinum on alumina oxidation catalyst produced sulfuric acid particles about 12 nm in size after a short-term operation. 1000 hours of sulfur exposure would typically correspond to a particle counting instrument that has been in use for well over a year. 4. Vehicles qabaas
    Diesel exhaust was obtained from an automobile with a four-cylinder diesel engine and Euro 5 compliant tailpipe emissions fueled with less than 100 ppm sulfur fuel and Longlife synthetic engine oil from which all exhaust aftertreatment components had been removed. The exhaust gas was introduced into a constant volume sampling system using filtered air in the standard manner. From an engine operating at 2500 rpm, an exhaust sample was diluted 10 to 1 with HEPA filtered air and fed through the unit. The exit gas from the unit was taken over into a conventional CPC operating with n-butanol and a smaller particle size cut-off of less than 10 nm. The temperature of the unit was initially at room temperature and the number of particles counted corresponded to 6x107 to 1x108 particles per cc. The sample gas preheater and the heating block containing the unit were then turned on and allowed to rise to a controlled temperature of 350 ° C. Measurements were taken one hour later to ensure complete thermal equilibrium. The number of particles counted by the CPC had dropped enormously to effectively zero, indicating that a very high proportion of engine exhaust particulates was of a volatile nature.
    In another experiment, a 1.6-liter four-cylinder gasoline engine was used in an automobile with Euro Stage 3 compliant tailpipe emissions, fueled with regular low-sulfur gasoline, to obtain an exhaust sample from just ahead of the close-coupled three-way catalyst. Particle measurements were made with a Cambustion DMS500 Fast Particle Analyzer, which required a higher flow of test gas than the previously used CPC. The test gas was diluted 4-fold with HEPA-filtered air at the time of the sample, and a secondary dilution was made in the particle counter at a dilution ratio of 20 to 1, which is typically used. A very large number of particles were measured, corresponding to 3x10® particles per cc, while after passage through the unit of the invention at 350 ° C a much smaller number of solid particles was measured, corresponding to less than 5x106 particles per cc. These were believed to originate mainly from inorganic additives in engine oil.
    In laboratory tests, it is common to use propene as a model gas for diesel exhaust. This is used in the tests described below. A unit described above with outer dimensions of OD 19 mm and a length of 42 mm was configured in a test unit such that a gas stream containing 200, 500 or 1000 ppm propene in air with or without the addition of water, first via the oxidation part and then the sulfur absorption part was passed. This test should mimic the behavior when high levels of hydrocarbons are present in the exhaust gas, such as when late injection of fuel into an engine occurs during regeneration of a particulate matter filter and the exhaust gas is not diluted before quantifying its level of particulate matter , This could be the case with a transportable emission measuring instrument. The total gas flow was 96 liters / hour with no added water and 102 liters / hour when water (6.0%) was present, which is typical of what could be used in conjunction with a condensation particle counter. If there was no added water in the inlet gas, the test started at just above room temperature and the temperature was gradually increased until no more propene was detected in the effluent gas stream by means of a Fourier transform infrared spectrometer. The same instrument was used to confirm the entry concentration of the propene, which was adjusted and maintained by mass flow controllers. When water was added to the inlet gas mixture, the temperature was kept above the condensation point. The temperature at which no propene was detected in the exit gas was 140 ° C when 200 ppm propene was present in the inlet gas, 150 ° C when 500 ppm propene was present in the inlet gas, and 170 ° C when 1000 ppm propene was in the inlet gas were present. The addition of water (6.0%) to the inlet gas caused an increase of about 5 ° C at each of these temperatures. Tests with the smaller 25.3 mm long, 17.9 mm diameter, high open end diameter metal foil unit similarly configured in the test equipment gave similar results with complete elimination of propene at 145 ° C. 155 ° C and 177 ° C, respectively, confirming that when operating at temperatures above 250 ° C, and especially above 300 ° C, all the hydrocarbons in the vapor phase are oxidized by each of the two units, thus preventing hydrocarbon nucleation becomes.
    权利要求:
    Claims (7)
    [1]
    claims:
    An improved nanoparticle counter having a gas treatment stage in front of a nanoparticle counter, the gas treatment stage comprising an oxidation catalyst and an absorber effective in absorbing gaseous sulfur compounds and, desirably, nitrogen oxides which, when cooled, nucleate and form particles, are effective Gas treatment step is applied to one or more flow monoliths, characterized in that the gas treatment step is applied to a metal foil monolith having not more than 400 cells / inch2 and a film thickness of not more than 50 microns and with an open area of at least 90%.
    [2]
    The instrument according to claim 1, wherein the monolithic film thickness is not more than 20 micrometers.
    [3]
    The instrument according to claim 1 or 2, wherein the gas treatment step comprises a catalyst selected from platinum, palladium, rhodium, gold and mixtures thereof.
    [4]
    An instrument according to any one of the preceding claims wherein the gas treatment step comprises an absorber selected from alkali metal compounds and alkaline earth metal compounds.
    [5]
    The instrument of any one of the preceding claims, wherein the gas treatment step comprises a downstream zone in which catalyst and absorber are mixed.
    [6]
    The instrument of any one of the preceding claims, wherein the gas treatment step comprises a zone comprising an inner layer of oxidation catalyst and an outermost layer of absorber.
    [7]
    A method of counting solid nanoparticles in an exhaust stream using a particle counting instrument comprising a gas treatment step comprising oxidizing volatile organic materials, then subsequently absorbing the sulfur materials from the gas phase, using a unit as claimed in any one of the preceding claims ,
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1317744.9A|GB201317744D0|2013-10-08|2013-10-08|Improvements in nanoparticle counting|
    PCT/GB2014/000397|WO2015052463A1|2013-10-08|2014-10-06|Improvements in nanoparticle counting|
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